Methods for producing mesoporous zeolite multifunctional catalysts for upgrading pyrolysis oil

ABSTRACT

A method of making a multifunctional catalyst for upgrading pyrolysis oil includes contacting a hierarchical mesoporous zeolite support with a solution including at least a first metal catalyst precursor and a second metal catalyst precursor, each or both of which may include a heteropolyacid. The hierarchical mesoporous zeolite support may have an average pore size of from 2 nm to 40 nm. Contacting the hierarchical mesoporous zeolite support with the solution deposits or adsorbs the first metal catalyst precursor and the second catalyst precursor onto outer surfaces and pore surfaces of the hierarchical mesoporous zeolite support to produce a multifunctional catalyst precursor. The method further includes removing excess solution and calcining the multifunctional catalyst precursor to produce the multifunctional catalyst comprising at least a first metal catalyst and a second metal catalyst deposited on the outer surfaces and pore surfaces of the hierarchical mesoporous zeolite support.

TECHNICAL FIELD

The present specification generally relates to multifunctional catalystsand methods for producing the multifunctional catalysts for upgradingpyrolysis oil.

BACKGROUND

Crude oil can be converted to valuable chemical intermediates andproducts through one or more hydrotreating processes. The hydrotreatingprocesses can include steam cracking, in which larger hydrocarbons inthe crude oil are cracked to form smaller hydrocarbons. Steam crackingunits produce a bottom stream, which is referred to as pyrolysis oil.The pyrolysis oil may include an increased concentration of aromaticcompounds compared to the crude oil feedstock. In many crude oilprocessing facilities, this pyrolysis oil is burned as fuel. However,the aromatic compounds in the pyrolysis oil can be converted to valuablechemical intermediates and building blocks. For example, aromaticcompounds from the pyrolysis oil can be converted into xylenes, whichcan be initial building blocks for producing terephthalic acid, whichcan then be used to produce polyesters. The aromatic compounds in thepyrolysis oil can be used to produce many other valuable aromaticintermediates. The market demand for these valuable aromaticintermediates continues to grow.

SUMMARY

Accordingly, ongoing needs exist for improved multifunctional catalystsfor upgrading pyrolysis oils. Pyrolysis oils from steam crackingprocesses can be upgraded to produce valuable aromatic intermediates bycontacting the pyrolysis oil with catalysts operable to convertmulti-ring aromatic compounds in the pyrolysis oil to one or more C6-C8aromatic compounds, which can include benzene, toluene, ethylbenzene,xylenes, other aromatic compounds, or combinations of these. Existingcatalysts operable to upgrade pyrolysis oil can include multi-metalhydrocracking catalysts that have 2 or more metals supported on acatalyst support. These multi-metal hydrocracking catalysts aretypically prepared from conventional metal precursors, such as metallatehydrates, metal nitrates, and other conventional metal precursorsimpregnated onto the microporous catalyst supports.

With these multi-metal hydrocracking catalysts prepared fromconventional metal precursors, large aromatic compounds (greater than 8carbon atoms) can be converted to C6-C8 aromatic compounds at reactiontemperatures in a range of 380 degrees Celsius (° C.) to 400° C. andpressures of from 6 megapascals (MPa) to 8 MPa. Maintaining the pressurein a range of 6 MPa to 8 MPa may require a greater pressure resistanceof the facility and may consume a greater amount of energy compared tolesser pressure systems. In other words, the use of existing multi-metalhydrocracking catalyst to upgrade pyrolysis oil requires expensiveequipment rated for greater operating pressures and can consume greateramounts of energy to maintain the pressure above 6 MPa. Reducing thepressure below 6 MPa can substantially reduce the yield of C6-C8aromatics when upgrading using these existing multi-metal hydrocrackingcatalysts prepared from conventional metal catalyst precursors.

Additionally, these conventional multi-metal hydrocracking catalysts maybe prepared using zeolite supports, which may generally be microporoushaving an average pore size of less than about 2 nanometers (nm).However, the multi-ring aromatic compounds present in pyrolysis oil mayhave molecular sizes that are larger than the average pore size ofzeolite supports used to prepare these conventional multi-metalcatalysts. Thus, the small average pore size of the nanoporous zeolitesmay restrict access of the larger multi-ring aromatic compounds toreactive sites within the pores of the zeolite support, thus, reducingthe yield and conversion attainable with these existing multi-metalhydrocracking catalysts.

The present disclosure is directed to multifunctional catalysts forupgrading pyrolysis oil. The multifunctional catalysts of the presentdisclosure are prepared from a hierarchical mesoporous zeolite support,and a heteropolyacid may be used for at least one of the metalprecursors. The present disclosure is also directed to methods of makingthe multifunctional catalyst and methods of upgrading pyrolysis oilusing the multifunctional catalyst. The multifunctional catalyst of thepresent disclosure may produce greater yields of C6-C8 aromaticcompounds from upgrading pyrolysis oil at reduced reaction pressurescompared to upgrading pyrolysis oil using existing multi-metalhydrocracking catalysts. The multifunctional catalyst of the presentdisclosure can be prepared by contacting a hierarchical mesoporouszeolite support with a solution containing a first metal catalystprecursor and a second metal catalyst precursor, where at least one ofthe first or second metal catalyst precursor is a heteropolyacid. Thehierarchical mesoporous zeolite support may have an average pore size offrom 2 nm to 40 nm.

The heteropolyacid is a compound that may include at least an acidichydrogen, a transition metal, at least one heteroatom, and oxygen. Ithas been discovered that preparing the multifunctional catalyst using aheteropolyacid for at least one of the metal precursors in place of aconventional metal precursor produces a multifunctional catalyst thatachieves a greater yield of C6-C8 aromatic compounds at reduced reactionpressures compared to the multi-metal hydrocracking catalysts that arecurrently used to upgrade pyrolysis oil. It has also been discoveredthat preparing the multifunctional catalyst from a hierarchicalmesoporous zeolite support may further increase the yield of C6-C8aromatic compounds at reduced reaction pressures. The improved yield andreduced operating pressure may increase the efficiency of upgradingpyrolysis oil and may reduce the capital and operating costs of theprocess for upgrading pyrolysis oil.

According to one or more aspects of the present disclosure, a method forproducing a multifunctional catalyst for upgrading pyrolysis oil mayinclude contacting a hierarchical mesoporous zeolite support with asolution comprising at least a first metal catalyst precursor and asecond metal catalyst precursor. The hierarchical mesoporous zeolitesupport may have an average pore size of from 2 nanometers to 40nanometers as determined by Barrett-Joyner-Halenda (BJH) analysis. Thefirst metal catalyst precursor, the second metal catalyst precursor, orboth, may include a heteropolyacid. The contacting may deposit the firstmetal catalyst precursor and the second catalyst precursor onto outersurfaces and pore surfaces of the hierarchical mesoporous zeolitesupport to produce a multifunctional catalyst precursor. The method mayfurther include removing excess solution from the multifunctionalcatalyst precursor and calcining the multifunctional catalyst precursorto produce the multifunctional catalyst comprising at least a firstmetal catalyst and a second metal catalyst deposited on the outersurfaces and pore surfaces of the hierarchical mesoporous zeolitesupport.

According to one or more other aspects of the present disclosure, amulti-functional catalyst for upgrading pyrolysis oil may be produced bya process that includes contacting a hierarchical mesoporous zeolitesupport with a solution comprising at least a first metal catalystprecursor and a second metal catalyst precursor. The hierarchicalmesoporous zeolite support may have an average pore size of from 2nanometers to 40 nanometers as determined by Barrett-Joyner-Halenda(BJH) analysis, the first metal catalyst precursor, the second metalcatalyst precursor, or both, may comprise a heteropolyacid, and thecontacting may deposit the first metal catalyst precursor and the secondcatalyst precursor onto outer surfaces and pore surfaces of thehierarchical mesoporous zeolite support to produce a multifunctionalcatalyst precursor. The process may further include removing excesssolution from the multifunctional catalyst precursor and calcining themultifunctional catalyst precursor to produce the multifunctionalcatalyst. The multifunctional catalyst may include at least a firstmetal catalyst and a second metal catalyst deposited on the outersurfaces and the pore surfaces of the zeolite support.

According to one or more other aspects of the present disclosure, amulti-functional catalyst for upgrading pyrolysis oil may include one ormore cobalt compounds, one or more molybdenum compounds, and phosphoroussupported on a hierarchical mesoporous zeolite support. At least one ofthe molybdenum compounds, cobalt compounds, or phosphorous may beprovided by a heteropolyacid precursor, and the hierarchical mesoporouszeolite support may have an average pore size of from 2 nanometers to 40nanometers as determined by BJH analysis.

According to still other aspects of the present disclosure, a method forupgrading pyrolysis oil may include contacting the pyrolysis oil with amultifunctional catalyst at mild reaction conditions comprising reactiontemperatures of less than 500 degrees Celsius (° C.) and pressures lessthan 6 megapascals (MPa). The pyrolysis oil may include multi-ringaromatic compounds. The multifunctional catalyst may be produced by aprocess comprising contacting a hierarchical mesoporous zeolite supportwith a solution comprising at least a first metal catalyst precursor anda second metal catalyst precursor. The hierarchical mesoporous zeolitesupport may have an average pore size of from 2 nanometers to 40nanometers as determined by Barrett-Joyner-Halenda (BJH) analysis, thefirst metal catalyst precursor, the second metal catalyst precursor, orboth, may include a heteropolyacid, and the contacting may deposit thefirst metal catalyst precursor and the second catalyst precursor ontoouter surfaces and pore surfaces of the hierarchical mesoporous zeolitesupport to produce a multifunctional catalyst precursor. The process forproducing the multifunctional catalyst may further include removingexcess solution from the multifunctional catalyst precursor andcalcining the multifunctional catalyst precursor to produce themultifunctional catalyst. The multifunctional catalyst comprises atleast a first metal catalyst and a second metal catalyst supported onthe zeolite support. Contact of the pyrolysis oil with themultifunctional catalyst at the reaction conditions may convert at leasta portion of the multi-ring aromatic compounds in the pyrolysis oil toone or more C6-C8 aromatic compounds.

Additional features and advantages of the described embodiments will beset forth in the detailed description, which follows, and in part willbe readily apparent to those skilled in the art from that description orrecognized by practicing the described embodiments, including thedetailed description, which follows, the claims, as well as the appendeddrawings.

BRIEF DESCRIPTION OF THE DRAWINGS

The following detailed description of specific embodiments of thepresent disclosure can be best understood when read in conjunction withthe following drawings, in which like structure is indicated with likereference numerals and in which:

FIG. 1 schematically depicts a reactor system for upgrading pyrolysisoil, according to one or more embodiments described in this disclosure;

FIG. 2 graphically depicts an example composition for pyrolysis oilobtained from a steam cracking process for steam cracking crude oil,according to one or more embodiments described in this disclosure; and

FIG. 3 schematically depicts a reactor system for upgrading a modelpyrolysis oil in the Examples, according to one or more embodimentsdescribed in this disclosure.

For the purposes of describing the simplified schematic illustrationsand descriptions of FIGS. 1 and 3, the numerous valves, temperaturesensors, flow meters, pressure regulators, electronic controllers,pumps, and the like that may be employed and well known to those ofordinary skill in the art of certain chemical processing operations arenot included. Further, accompanying components that are often includedin typical chemical processing operations, such as valves, pipes, pumps,agitators, heat exchangers, instrumentation, internal vessel structures,or other subsystems may not be depicted. Though not depicted, it shouldbe understood that these components are within the spirit and scope ofthe present embodiments disclosed. However, operational components, suchas those described in the present disclosure, may be added to theembodiments described in this disclosure.

Arrows in the drawings refer to process streams. However, the arrows mayequivalently refer to transfer lines, which may serve to transferprocess streams between two or more system components. Additionally,arrows that connect to system components may define inlets or outlets ineach given system component. The arrow direction corresponds generallywith the major direction of movement of the materials of the streamcontained within the physical transfer line signified by the arrow.Furthermore, arrows that do not connect two or more system componentsmay signify a product stream which exits the depicted system or a systeminlet stream which enters the depicted system. Product streams may befurther processed in accompanying chemical processing systems or may becommercialized as end products.

Additionally, arrows in the drawings may schematically depict processsteps of transporting a stream from one system component to anothersystem component. For example, an arrow from one system componentpointing to another system component may represent “passing” a systemcomponent effluent to another system component, which may include thecontents of a process stream “exiting” or being “removed” from onesystem component and “introducing” the contents of that product streamto another system component.

It should be understood that two or more process streams are “mixed” or“combined” when two or more lines intersect in the schematic flowdiagrams of FIGS. 1 and 3. Mixing or combining may also include mixingby directly introducing both streams into a like system component, suchas a separation unit, reactor, or other system component. For example,it should be understood that when two streams are depicted as beingcombined directly prior to entering a system component, the streamscould equivalently be introduced into the system component separatelyand be mixed in the system component.

Reference will now be made in greater detail to various embodiments,some embodiments of which are illustrated in the accompanying drawings.Whenever possible, the same reference numerals will be used throughoutthe drawings to refer to the same or similar parts.

DETAILED DESCRIPTION

Embodiments of the present disclosure are directed to multifunctionalcatalysts for upgrading pyrolysis oil. The multifunctional catalysts mayinclude a plurality of metal catalysts supported on a hierarchicalmesoporous zeolite support. The hierarchical mesoporous zeolite supportmay have an average pore size of from 2 nanometers (nm) to 40 nm, orfrom 5 nm to 25 nm. In some embodiments, the hierarchical mesoporouszeolite support may be a hierarchical mesoporous beta zeolite support.The multifunctional catalysts of the present disclosure can be preparedusing a heteropolyacid for at least one of the metal catalystprecursors. The multifunctional catalysts for upgrading pyrolysis oil ofthe present disclosure made using heteropolyacids for the metal catalystprecursors and having a hierarchical mesoporous zeolite support mayprovide greater yield of valuable aromatic compounds, such as benzene,toluene, ethylbenzene, and xylenes, from upgrading of the pyrolysis oil.Additionally, the multifunctional catalysts for upgrading pyrolysis oilmay enable the upgrading of pyrolysis oil to be conducted at lesserreaction pressures compared to existing commercially available catalystsfor upgrading pyrolysis oil.

As used in this disclosure, the term “C6-C8 aromatic compounds” mayrefer to one or more compounds having an aromatic ring, with or withoutsubstitution, and from 6 to 8 carbon atoms. The term “BTEX” may refer toany combination of benzene, toluene, ethylbenzene, para-xylene,meta-xylene, and ortho-xylene.

As used in this disclosure, the term “xylenes,” when used without adesignation of the isomer, such as the prefix para, meta, or ortho, mayrefer to one or more of meta-xylene, ortho-xylene, para-xylene, andmixtures of these xylene isomers.

As used in this disclosure, the terms “upstream” and “downstream” referto the relative positioning of unit operations with respect to thedirection of flow of the process streams. A first unit operation of asystem is considered “upstream” of a second unit operation if processstreams flowing through the system encounter the first unit operationbefore encountering the second unit operation. Likewise, a second unitoperation is considered “downstream” of the first unit operation if theprocess streams flowing through the system encounter the first unitoperation before encountering the second unit operation.

As used in this disclosure, the term “outer surfaces” may refer tosurfaces at the outer periphery of a catalyst or catalyst support, suchas the hierarchical mesoporous zeolite support.

As used in this disclosure, the term “pore surfaces” may refer to theinner surfaces of pores in a catalyst or catalyst support, where thepores include at least the pores in fluid communication with the outersurfaces of the catalyst or catalyst support and are accessible toreactants.

As used in this disclosure, the “average pore size” of a catalyst orcatalyst support may refer to the average pore size determined byBarrett-Joyner-Halenda (BJH) analysis. BJH analysis measures the amountof a gas (argon) that detaches from a material, such as the hierarchicalmesoporous zeolite support, at 87 Kelvin over a range of pressures.Using the Kelvin equation, the amount of argon adsorbate removed fromthe pores of the material and the relative pressure of the system can beused to calculate the average pore size of the material.

Referring now to FIG. 1, a system 10 for upgrading pyrolysis oil 12 isschematically depicted. The system 10 for upgrading pyrolysis oil 12 mayinclude a reactor unit 20 and a separation unit 30 downstream of thereactor unit 20. The reactor unit 20 may include one or a plurality ofreactors and may be operable to contact the pyrolysis oil 12 with acatalyst in reaction zone 14 to produce an upgraded effluent 22. Thecatalyst may be the multifunctional catalyst of the present disclosure.The upgraded effluent 22 may be passed to the separation unit 30, whichmay include one or a plurality of separation processes or unitoperations. The separation unit 30 may be operable to separate theupgraded effluent 22 into one or a plurality of product streams, such asa BTEX-containing stream and a greater boiling fraction 34. Although theseparation unit 30 is depicted in FIG. 1 as separating the upgradedeffluent 22 into the C6-C8 aromatic stream 32 and a greater boilingfraction 34, it is understood that the separation unit 30 may beoperable to separate the upgraded effluent 22 into a plurality ofproduct streams, one of which may include a C6-C8 aromatic stream 32.

The pyrolysis oil 12 may be a stream from a hydrocarbon processingfacility that is rich in aromatic compounds, such as multi-ring aromaticcompounds. In some embodiments, the pyrolysis oil may be a bottom streamfrom a steam cracking process. The pyrolysis oil 12 may includemono-aromatic compounds and multi-aromatic compounds. Multi-aromaticcompounds may include aromatic compounds including 2, 3, 4, 5, 6, 7, 8,or more than 8 aromatic ring structures. The pyrolysis oil 12 may alsoinclude other components, such as but not limited to saturatedhydrocarbons. Referring to FIG. 2, the composition of a typicallypyrolysis oil produced from steam cracking crude oil from Saudi Arabiais depicted. As shown in FIG. 2, the pyrolysis oil may includemono-aromatics, di-aromatics, tri-aromatics, tetra-aromatics,penta-aromatics, hexa-aromatics, and aromatic compounds having 7 or morearomatic rings (hepta & plus aromatics in FIG. 2). The pyrolysis oil mayinclude elevated concentrations of di-aromatic compounds and aromaticcompounds having greater than or equal to 7 aromatic rings, as indicatedby FIG. 2. In some embodiments, the pyrolysis oil that is rich inmulti-aromatic compounds may include greater than or equal to 50 weightpercent (wt. %) multi-aromatic compounds, such as greater than or equalto 60 wt. %, greater than or equal to 65 wt. %, greater than or equal to70 wt. %, greater than or equal to 75 wt. %, or even greater than orequal to 80 wt. % multi-aromatic compounds based on the unit weight ofthe pyrolysis oil. The pyrolysis oil may also have a low concentrationof sulfur and sulfur compounds. The pyrolysis oil may have aconcentration of sulfur and sulfur-containing compounds of less than orequal to 500 parts per million by weight (ppmw), such as less than orequal to 400 ppmw, or even less than or equal to 300 ppmw.

The multi-aromatic compounds in the pyrolysis oil may be upgraded toC6-C8 aromatic compounds through contact with the catalyst at thereaction temperature and pressure. Converting di-aromatic andmulti-aromatic compounds to C6-C8 aromatic compounds, such as benzene,toluene, ethylbenzene, and xylenes, is a complicated reaction that mayinclude multiple synchronized and selective reactions, which may includeselective hydrogenation of one aromatic ring in a compound but not all,subsequent ring opening of the saturated naphthenic ring,hydro-dealkylation, and transalkylation. For example, in one embodiment,upgrading pyrolysis oil may include selective hydrogenation of at leastone aromatic ring structure or a multi-ring aromatic compound to producea molecule with one or more aromatic rings and at least one saturatedring. The saturated ring portion may then undergo ring opening toproduce a substituted aromatic. The substituted aromatic may thenundergo one or more of hydroalkylation, transalkylation, ordisproportionation to produce C6-C8 aromatic compounds. It is understoodthat multiple variations and combinations of these reactions as well asother chemical reactions may occur during the upgrading process.

This complex sequence of synchronized reactions for upgrading pyrolysisoil may be catalyzed using a multi-metallic catalyst having at leastcatalytic transition metals. In conventional upgrading processes, thecatalyst used to upgrade the pyrolysis oil may be a multi-metalhydrocracking catalyst. These multi-metal hydrocracking catalysts areoften synthesized using conventional metal precursors, such as metallatehydrates, metal nitrates, metal carbonates, metal hydroxides, otherconventional metal precursors, or combinations of these conventionalmetal precursors.

With these multi-metal hydrocracking catalysts made from conventionalmetal precursors, large aromatic compounds (greater than 8 carbon atoms)can be converted to C6-C8 aromatic compounds, such as but not limited tobenzene, toluene, ethylbenzene, or xylenes (BTEX), at reactiontemperatures in a range of 380 degrees Celsius (° C.) to 400° C. andpressures of from 6 megapascals (MPa) to 8 MPa. Maintaining the pressurein a range of 6 MPa to 8 MPa may require a greater pressure resistanceof the facility and may consume a greater amount of energy compared toreactions conducted a lesser reaction pressures. In other words, the useof existing multi-metal hydrocracking catalysts to upgrade pyrolysis oilmay require expensive equipment, which is rated for greater operatingpressures, and can consume greater amounts of energy to maintain thepressure above 6 MPa. Additionally, the yield of C6-C8 aromaticcompounds using these existing multi-metal hydrocracking catalysts islow. Reducing the pressure below 6 MPa can further reduce the yield ofC6-C8 aromatic compounds when upgrading using existing multi-metalhydrocracking catalysts.

Additionally, these conventional multi-metal hydrocracking catalysts maybe prepared using zeolite supports, which may generally be microporousmaterials having an average pore size of less than about 2 nm or evenless than about 1 nm as determined using the BJH method. However, themulti-ring aromatic compounds present in pyrolysis oil may havemolecular sizes that are larger than the average pore size of zeolitesupports used to prepare these conventional multi-metal catalysts. Forexample, a typical beta zeolite support may have an average pore size ofabout 6.7 angstroms (Å), which is smaller than the molecular size oftri-aromatic compounds (8.171 Å), tetra-aromatic compounds (8.562 Å),and penta-aromatic compounds (8.577 Å). The molecular sizes of thetri-aromatic, tetra-aromatic, and penta-aromatic compounds are providedfor the molecules without any substitution on the aromatic rings. Thesmall average pore size of the nanoporous zeolites may restrict accessof the larger multi-ring aromatic compounds to reactive sites within thepores of the zeolite support, thus, reducing the yield and conversionthat is attainable with these catalysts.

As previously discussed, the present disclosure is directed to amultifunctional catalyst for upgrading pyrolysis oil, themultifunctional catalyst being produced by depositing a plurality ofmetal catalysts onto at least the outer surfaces and pore surfaces of ahierarchical mesoporous zeolite support, where at least one of the metalcatalysts is provided by a heteropolyacid utilized as a metal catalystprecursor. The present disclosure is also directed to themultifunctional catalysts prepared by the disclosed methods and methodsof upgrading pyrolysis oil using the disclosed multifunctionalcatalysts. The methods of the present disclosure for making themultifunctional catalyst for upgrading pyrolysis oil may includecontacting the hierarchical mesoporous zeolite support with a solutioncomprising at least a first metal catalyst precursor and a second metalcatalyst precursor. The first metal catalyst precursor, the second metalcatalyst precursor, or both, may include a heteropolyacid. Thehierarchical mesoporous zeolite support may have an average pore size offrom 2 nm to 40 nm, or from 5 nm to 25 nm as determined using the BJHmethod. Contacting the hierarchical mesoporous zeolite support with thesolution may result in deposition or adsorption of the first metalcatalyst precursor and the second catalyst precursor onto outer surfacesand pore surfaces of the hierarchical mesoporous zeolite support toproduce a multifunctional catalyst precursor. The method may furtherinclude removing the excess solution and solvent from themultifunctional catalyst precursor and calcining the multifunctionalcatalyst precursor to produce the multifunctional catalyst, whichincludes at least a first metal catalyst and a second metal catalystdeposited on the outer surfaces and pore surfaces of the zeolitesupport.

The multifunctional catalysts made by the methods of the presentdisclosure may increase the yield of BTEX from upgrading pyrolysis oilcompared to existing multi-metal hydrocracking catalysts. Additionally,as compared to existing multi-metal hydrocracking catalysts, themultifunctional catalysts made by the methods of the present disclosuremay also enable the process for upgrading pyrolysis oil to be conductedat the same reaction temperature and reduced reaction pressure, such asa reaction pressure less than or equal to 5 MPa. The reduced reactionpressure enabled by the multifunctional catalysts of the presentdisclosure may reduce the capital and operating costs of systems forupgrading pyrolysis oils.

The method of making the multi-functional catalysts may includeproviding a hierarchical mesoporous zeolite support. The hierarchicalmesoporous zeolite support may have an average pore size sufficient toenable multi-ring aromatic compounds to access reactive sites within thepores of the hierarchical mesoporous zeolite support. The hierarchicalmesoporous zeolite support may have an average pore size of greater thanor equal to 2 nm, greater than or equal to 5 nm, or even greater than orequal to 8 nm as determined using the BJH method. The hierarchicalmesoporous zeolite support may have an average pore size less than orequal to 40 nm, less than or equal to 30 nm, or even less than or equalto 25 nm as determined using the BJH method. In some embodiments, thehierarchical mesoporous zeolite support may have an average pore size offrom 2 nm to 40 nm, from 2 nm to 30 nm, from 2 nm to 25 nm, from 5 nm to40 nm, from 5 nm to 30 nm, from 5 nm to 25 nm, from 8 nm to 40 nm, from8 nm to 30 nm, or from 8 nm to 25 nm, where the average pore size isdetermined using the BJH method.

The hierarchical mesoporous zeolite support may have a molar ratio ofsilica (SiO₂) to alumina (Al₂O₃) of greater than or equal to 10, such asgreater than or equal to 20, greater than or equal to 30, greater thanor equal to 40, greater than or equal to 50, or greater than or equal to60. The zeolite support may have a molar ratio of SiO₂ to Al₂O₃ of lessthan or equal to 70, such as less than or equal to 60, less than orequal to 50, less than or equal to 40, less than or equal to 30, or evenless than or equal to 20. The zeolite support may have a molar ratio ofSiO₂ to Al₂O₃ of from 10 to 70. In some embodiments, the zeolite supportmay have a molar ratio of SiO₂ to Al₂O₃ of from 10 to 60, from 10 to 50,from 10 to 40, from 20 to 70, from 20 to 60, from 20 to 50, from 20 to40, from 30 to 70, from 30 to 60, from 30 to 50, from 40 to 70, from 40to 60, from 50 to 70, or from 10 to 30. In some embodiments, thehierarchical mesoporous zeolite support may be a hierarchical mesoporousbeta zeolite support. In some embodiments, the hierarchical mesoporousbeta zeolite support may have an average pore size of 2 nm to 40 nm, orfrom 5 nm to 25 nm.

The hierarchical mesoporous zeolite support may be prepared from aparent microporous zeolite through a desilication process, in whichsilica may be removed from the zeolite to increase the average poresize. A desilication method of preparing the hierarchical mesoporouszeolite support may include providing a microporous parent zeolite witha silica to alumina (SiO₂/Al₂O₃) ratio of at least 5 or greater than orequal to 20, mixing the microporous parent zeolite with an aqueous metalhydroxide solution, and heating the microporous parent zeolite andaqueous metal hydroxide mixture to temperatures greater than or equal to100° C. to produce the hierarchical mesoporous zeolite supports havingan average pore size greater than 2 nm, greater than or equal to 5 nm,or even greater than or equal to 8 nm as determined using the BJHmethod. In some embodiments, the hierarchical mesoporous zeolitesupports may be produced without a templating agent or a pore-directingagent.

As used in the present disclosure, microporous zeolites refer to zeoliteparticles that have an average pore size of less than 2 nm, such as lessthan 1 nm as determined using the BJH method. The microporous zeolitesmay have an average particle size, as measured by their longestdimension, of less than or equal to 100 nm. In some embodiments, themicroporous parent zeolite particles are present as a single crystalstructure. The microporous parent zeolites may have an average particlesize from 1 nm to 800 nm, from 1 nm to 650 nm, from 1 nm to 500 nm, from50 nm to 800 nm, from 100 nm to 800 nm, from 200 mm to 800 nm, from 200nm to 500 nm, from 300 nm to 800 nm, or from 50 nm to 600 nm. Theaverage particle size of a zeolite may refer to the average value of theparticle size of all the particles of a zeolite in a given sample. Insome embodiments, the microporous parent zeolite may have a molar ratioof silica to alumina (SiO₂/Al₂O₃) of at least 5, at least 15, at least20, at least 25, at least 30, or even at least 35. In some embodiments,the microporous parent zeolite may have a molar ratio of silica toalumina of from 5 to 100, from 5 to 90, from 5 to 80, from 20 to 100,from 20 to 90, from 20 to 80, from 20 to 70, from 20 to 66, from 25 to100, from 25 to 90, from 25 to 80, from 25 to 70, from 25 to 66, from 30to 100, from 30 to 90, from 30 to 80, from 30 to 70, from 30 to 66, from35 to 100, from 35 to 90, from 35 to 80, from 35 to 70, or even from 35to 66.

In some embodiments, the microporous parent zeolite may be a betazeolite. Providing the microporous parent zeolite may includesynthesizing or preparing the microporous parent zeolites. Processes forpreparing microporous parent zeolites may include, but are not limitedto, synthesizing the microporous parent zeolites or directly acquiringthe microporous parent zeolites from another source. It should beunderstood that multiple methods known in the art may be available tosynthesize the microporous parent zeolites. In some embodiments,providing the microporous parent zeolites may include providing acolloidal mixture comprising the microporous parent zeolites, silica,alumina, and water.

Desilication methods for producing hierarchical mesoporous zeolitesupports may further include contacting the microporous parent zeoliteswith an aqueous metal hydroxide solution. The aqueous metal hydroxidesolution may include a single metal hydroxide species, or may be acombination of two or more metal hydroxide chemical species. In someembodiments, the aqueous metal hydroxide solution comprises at least onealkali metal hydroxide, at least one alkaline earth metal hydroxide, orcombinations thereof. In other embodiments, the aqueous metal hydroxidesolution may comprise LiOH, NaOH, KOH, RbOH, Mg(OH)₂, Ca(OH)₂, Sr(OH)₂,Ba(OH)₂, or combinations thereof. In some embodiments, contacting themicroporous parent zeolite with the aqueous metal hydroxide solution mayinclude mixing the combined mixture of the microporous parent zeoliteand aqueous metal hydroxide.

The aqueous metal hydroxide solution may have a molar concentration ofthe metal hydroxide of from 0.01 moles per liter (M) to 10 M. In otherembodiments, the aqueous metal hydroxide solution may have a molarconcentration of the metal hydroxide of from 0.01 M to 5 M, from 0.01 Mto 3 M, from 0.01 M to 1 M, from 0.05 M to 1 M, from 0.05 M to 0.8 M,from 0.05 M to 0.5 M, or even from 0.1 M to 0.4 M. In one or moreembodiments, the combined mixture of the microporous parent zeolite andaqueous metal hydroxide may have a pH greater than or equal to 12 oreven greater than or equal to 13. In some embodiments, the combinedmixture of the microporous parent zeolite and aqueous metal hydroxidemay have a pH of from 12 to 14 or even from 13 to 14.

The desilication methods for producing hierarchical mesoporous zeolitesupports may further include heating the parent beta zeolite and aqueousmetal hydroxide mixture. The heating may occur at temperatures greaterthan or equal to 100° C., greater than or equal to 125° C., greater thanor equal to 150° C., greater than or equal to 175° C., or even greaterthan or equal to 200° C. The heating may occur at temperatures less thanor equal to 500° C., less than or equal to 400° C., less than or equalto 300° C., or even less than or equal to 250° C. In some embodiments,the heating may occur at temperatures of from 100° C. to 500° C., from125° C. to 500° C., from 150° C. to 500° C., from 175° C. to 500° C.,from 200° C. to 500° C., from 250° C. to 500° C., from 100° C. to 400°C., from 100° C. to 300° C., from 100° C. to 250° C., from 125° C. to300° C., from 150° C. to 300° C., or from 125° C. to 250° C. The parentbeta zeolite and aqueous metal hydroxide mixture may be heated for atime interval of greater than or equal to 1 hour, greater than or equalto 4 hours, greater than or equal to 16 hours, greater than or equal to18 hours, or even greater than or equal to 24 hours. In someembodiments, the parent beta zeolite and aqueous metal hydroxide mixturemay be heated for a time interval of from 1 hour to 16 hours, from 4hours to 16 hours, from 16 hours to 48 hours, from 16 hours to 30 hours,from 16 hours to 24 hours, from 18 hours to 48 hours, from 18 hours to30 hours, from 18 hours to 24 hours, or from 24 hours to 48 hours.Following heating, the aqueous metal hydroxide mixture may be removedand the desilicated zeolite. The desilicated parent zeolite may bewashed to remove excess metal hydroxide and may then be dried to producethe hierarchical mesoporous zeolite.

The desilication methods disclosed herein for producing the hierarchicalmesoporous zeolite support may produce hierarchical mesoporous zeolitesupports having an average pore size greater than 2 nm, greater than orequal to 4 nm, or even greater than or equal to 8 nm. As previouslydiscussed, the average pore size of the hierarchical mesoporous zeolitesupport can be determine by Barrett-Joyner-Halenda (BJH) analysis. BJHanalysis measures the amount of a gas (argon) that detaches from amaterial, such as the hierarchical mesoporous zeolite support, at 87Kelvin over a range of pressures. Using the Kelvin equation, the averagepore size of the material can be calculated from the amount of argonadsorbate removed from the pores of the material and the relativepressure of the system. The desilication methods may producehierarchical mesoporous zeolite supports having an average pore sizefrom 2 nm to 40 nm, from 2 nm to 30 nm, from 2 nm to 25 nm, from 5 nm to40 nm, from 5 nm to 30 nm, from 5 nm to 25 nm, from 8 nm to 40 nm, from8 nm to 30 nm, or from 8 nm to 25 nm, from 8 nm to 20 nm, from 10 nm to25 nm, from 10 nm to 20 nm, from 12 nm to 25 nm, from 12 nm to 20 nm,from 8 nm to 18 nm, from 8 nm to 16 nm, or from 12 nm to 18 nm, asdetermined from BJH analysis.

The Non-Local Density Functional Theory (NLDFT) method can determine thetotal pore volume of the hierarchical mesoporous zeolite support fromthe adsorption data. The NLDFT method takes into account the roughsurface area of crystalline silica materials. The desilication methodmay produce a hierarchical mesoporous zeolite support having a totalpore volume greater than or equal to 0.35 cubic centimeters per gram(cm³/g), greater than or equal to 0.4 cm³/g, greater than or equal to0.45 cm³/g, or even greater than or equal to 0.5 cm³/g, determinedaccording to the NLDFT method.

Without intending to be limited by any particular theory, it is believedthat upon contacting the microporous parent zeolite during the heatingprocess, the metal hydroxide solution may create the mesopores bypreferentially extracting silicon from the zeolite framework (also knownas desilication). When the temperature is above 100° C. and the pressureis above ambient atmospheric pressure, the synthetic conditions becomesimilar to the conventional bottom-up approach that favorscrystallization of zeolites. During this desilication process, aluminapresent in the zeolite may aid in achieving hierarchical mesoporeformation while preserving zeolite crystallinity. Not intending to belimited by any particular theory, it is believed that the alumina in thezeolite framework may prevent excessive silicon extraction by the metalhydroxide solution and may maintain a zeolite framework withlocally-desilicated areas that can be recrystallized at the syntheticconditions. Therefore, the crystallinity of the resulting hierarchicalmesoporous zeolite supports can be preserved during the formation ofmesopores. The preservation of the crystallinity from the process may beverified by conducting X-Ray Diffraction (XRD) analysis of thehierarchical mesoporous zeolite support and the microporous parentzeolite and comparing the XRD plots for each. For a microporous parentzeolite exhibiting specific XRD peaks, a hierarchical mesoporous zeolitesupport produced from the microporous parent zeolite and havingpreserved crystallinity exhibits the same peaks and comparable peakintensities compared to the microporous parent zeolite. Maintaining thecrystallinity of the hierarchical mesoporous zeolite support compared tothe microporous parent zeolite may also preserve the acid reaction sitesof the hierarchical mesoporous zeolite support compared to themicroporous parent zeolite.

Although a desilication method for producing the hierarchical mesoporouszeolite support is described in detail, it is understood that any otherprocess known in the art may also be used to produce the hierarchicalmesoporous zeolite support. Methods for producing hierarchicalmesoporous zeolite supports may include, but are not limited to, other“top down” methods conducted at temperatures less than 100° C., whichmay include utilizing pore-directing agents to facilitate formation ofmesopores. “Top down” methods may refer to methods in which a parentzeolite is chemically eroded to produce the hierarchical mesoporousstructure. Another method for producing hierarchical mesoporous zeolitesupports may include “bottom up” methods, which including building upthe hierarchical mesoporous zeolite from zeolite precursors. In the“bottom up” methods, templating agents are included and the zeolite isbuilt-up around the templating agents to form the mesoporous structure.The resulting zeolite is then calcined to burn off the templating agentto produce the hierarchical mesoporous zeolite support. Other synthesismethods may also be used to produce the hierarchical mesoporous zeolite.

The multifunctional catalyst of the present disclosure for upgradingpyrolysis oil may be prepared from the hierarchical mesoporous zeolitesupport. The methods of preparing the multifunctional catalyst mayinclude wet impregnation of at least a first metal catalyst precursorand a second metal catalyst precursor onto the outer surfaces, poresurfaces, or both, of the hierarchical mesoporous zeolite support. Atleast one of the first metal catalyst precursor, the second metalcatalyst precursor, or both, is a heteropolyacid. The methods mayinclude contacting the hierarchical mesoporous zeolite support with thesolution that includes at least the first metal catalyst precursor, thesecond metal catalyst precursor, and a solvent. The solution may also,optionally, include a phosphorous-containing compound, such as when theheteropolyacid for the metal catalyst precursor does not includephosphorous.

The first metal catalyst precursor may include a first metal, and thesecond metal catalyst precursor may include a second metal differentfrom the first metal. The first metal and the second metal may betransition metals, such as, but not limited to transition metals inGroups 5, 6, 7, 8, 9, and 10 of the International Union of Pure andApplied Chemistry (IUPAC) periodic table of elements. In someembodiments, the first metal of the first metal catalyst precursor maybe a metal selected from cobalt, molybdenum, vanadium, or combinationsof these. In some embodiments, the second metal of the second metalcatalyst precursor may be a metal independently selected from cobalt,molybdenum, vanadium, or combinations of these, and may be differentfrom the first metal.

The first metal catalyst precursor, the second metal catalyst precursor,or both may be a heteropolyacid. The heteropolyacid may include one ormore than one metal selected from cobalt, molybdenum, or combinations ofcobalt and molybdenum; at least one heteroatom selected from phosphorous(P), silicon (Si), arsenic (Ar), germanium (Ge), or combinations ofthese; and one or more than one acidic hydrogen. As used in thisdisclosure, the term “acidic hydrogen” may refer to a hydrogen atom ofthe heteropolyacid that may have a tendency to dissociate from theheteropolyacid in solution to form a positive ion. The heteropolyacidmay also include oxygen. Heteropolyacids suitable for the first metalcatalyst precursor, the second metal catalyst precursor, or both mayhave a Keggin structure having general formula XM₁₂O₄₀ ^(n−) or a Dawsonstructure having the general formula XM₁₈O₈₂ ^(n−), in which X is theheteroatom selected from phosphorous, silicon, arsenic, germanium, orcombinations of these; M is the molybdenum and optionally one or more ofcobalt, vanadium, or combinations of these; and n− is an integerindicative of the charge of the anion of the heteropolyacid. Examples ofheteropolyacids may include, but are not limited to phosphormolybdicheteropolyacid (H₃PMo₁₂O₄₀), silicomolybdic heteropolyacid(H₄SiMo₁₂O₄₀), decamolybdiccobaltate heteropolyacid (H₆[Co₂Mo₁₀O₃₈H₄]),H₄[PCoMo₁₁O₄₀], H₄[PVMo₁₁O₄₀], H₅[PV₂Mo₁₀O₄₀], H₇[PV₄Mo₈O₄₀], H₉[PV₆Mo₆O₄₀], H₃[AsMo₁₂O₄₀], H₄[AsCoMo₁₁O₄₀], H₅[AsCo₂Mo₁₀O₄₀],H₄[AsVMo₁₁O₄₀], H₅[AsV₂Mo₁₀O₄₀], H₇[AsV₄Mo₈O₄₀], H₉[AsV₆Mo₆O₄₀],H₅[SiCoMo₁₁O₄₀], H₆[SiCO₂Mo₁₀O₄₀], H₅[SiVMo₁₁O₄₀], H₆[SiV₂Mo₁₀O₄₀],H₁₀[SiV₆Mo₆O₄₀], H₆[P₂Mo₁₈O₈₂], other heteropolyacids, salts of theseheteropolyacids, or combinations of heteropolyacids. Salts of theseheteropolyacids may include alkali metal salts, alkaline earth metalsalts, nitrate salts, sulfate salts, or other salts of theheteropolyacid. Alkali metals may include sodium, potassium, rubidium,caesium, or combinations of these. Alkaline earth metals may include,but are not limited to magnesium, calcium, or combinations of these. Insome embodiments, the heteropolyacid may include phosphormolybdicheteropolyacid having formula H₃[PMo₁₂O₄₀]. In some embodiments, theheteropolyacid may include decamolybdodicobaltate heteropolyacid havingchemical formula H₆[Co₂Mo₁₀O₃₈H₄]. In some embodiments, theheteropolyacid may be silicomolybdic heterpolyacid having chemicalformula H₄[SiMo₁₂O₄₀]. In some embodiments, the first metal catalystprecursor, the second catalyst precursor, or both may be a metal salt ofa heteropolyacid, such as an alkali metal salt or alkaline metal salt ofthe heteropolyacid.

As previously described in this disclosure, the first metal catalystprecursor, the second metal catalyst precursor, or both may be aheteropolyacid. In some embodiments, the first metal catalyst precursormay include a heteropolyacid, and the second metal catalyst precursormay include a non-heteropolyacid precursor. In some embodiments, boththe first metal catalyst precursor and the second metal catalystprecursor may include heteropolyacids. In some embodiments, the firstmetal catalyst precursor may include a first heteropolyacid, and thesecond metal catalyst precursor may include a second heteropolyacid thatis different from the first heteropolyacid. For example, in someembodiments, the first metal catalyst precursor may include a firstheteropolyacid that includes molybdenum as the metal, and the secondmetal catalyst precursor may include a second heteropolyacid thatincludes cobalt as the metal. In some embodiments, the first metalcatalyst precursor and the second metal catalyst precursor may includethe same heteropolyacid, and the heteropolyacid may include a firstmetal, a second metal that is different from the first metal, and atleast one heteroatom. For example, in some embodiments, the solution mayinclude decamolybdiccobaltate heteropolyacid having chemical formulaH₆[Co₂Mo₁₀O₃₈H₄], which includes both cobalt and molybdenum and mayserve as both the first metal catalyst precursor and the second metalcatalyst precursor.

In some embodiments, one of the first metal catalyst precursor or thesecond metal precursor may include a non-heteropolyacid metal catalystprecursor, such as a metallate hydrate, metal nitrate, and othernon-heteropolyacid precursor. The solution may also include aphosphorous-containing compound, such as, but not limited to, phosphoricacid, phosphorous acid, or other phosphorous-containing compounds, suchas when the heteroatom in the heteropolyacid is not phosphorous.

The first metal catalyst precursor and the second metal catalystprecursor may be dispersed or dissolved in a solvent to form thesolution. The solvent may be water. The solvent may additionally includeone or more organic solvents, such as but not limited to organicalcohols or other organic solvents. One or more than one of theheteropolyacids may be dehydrated prior to combining the heteropolyacidwith the solvent to produce the solution. The solution may have aconcentration of the first metal catalyst precursor sufficient to resultin the first metal catalyst precursor being deposited on or adsorbedonto the outer surfaces and pore surfaces of the zeolite support. Thesolution may have greater than or equal to 1 wt. %, greater than orequal to 2 wt. %, greater than or equal to 5 wt. % or even greater thanor equal to 10 wt. % first metal catalyst precursor based on the totalweight of the solution before contact with the zeolite support. Thesolution may have less than or equal to 20 wt. %, less than or equal to15 wt. %, or even less than or equal to 12 wt. % first metal catalystprecursor based on the total weight of the solution before contact withthe zeolite support. In some embodiments, the solution may include from1 wt. % to 20 wt. % of the first metal catalyst precursor, such as from1 wt. % to 15 wt. %, from 1 wt. % to 10 wt. %, from 1 wt. % to 5 wt. %,from 2 wt. % to 20 wt. %, from 2 wt. % to 15 wt. %, from 2 wt. % to 10wt. %, or from 2 wt. % to 5 wt. % first metal catalyst precursor basedon the total weight of the solution before contact with the zeolitesupport.

The solution may have a concentration of the second metal catalystprecursor sufficient to result in the second metal catalyst precursorbeing deposited on or adsorbed onto the outer surfaces and pore surfacesof the zeolite support. The solution may have greater than or equal to 1wt. %, greater than or equal to 2 wt. %, greater than or equal to 5wt. %or even greater than or equal to 10 wt. % second metal catalystprecursor based on the total weight of the solution before contact withthe zeolite support. The solution may have less than or equal to 20 wt.%, less than or equal to 15 wt. %, or even less than or equal to 12 wt.% second metal catalyst precursor based on the total weight of thesolution before contact with the zeolite support. In some embodiments,the solution may include from 1 wt. % to 20 wt. % of the second metalcatalyst precursor, such as from 1 wt. % to 15 wt. %, from 1 wt. % to 10wt. %, from 1 wt. % to 5 wt. %, from 2 wt. % to 20 wt. %, from 2 wt. %to 15 wt. %, from 2 wt. % to 10 wt. %, or from 2 wt. % to 5 wt. % secondmetal catalyst precursor based on the total weight of the solutionbefore contact with the zeolite support.

Once the solution is prepared, the hierarchical mesoporous zeolitesupport may be contacted with the solution at ambient conditions. Thesolution may be mixed for a period of time prior to contacting thehierarchical mesoporous zeolite support with the solution. The mixturecomprising the hierarchical mesoporous zeolite support dispersed in thesolution may be mixed for a period of time long enough to providesufficient adsorption or deposition of the first metal catalystprecursor and the second metal catalyst precursor onto the outersurfaces and pore surfaces of the hierarchical mesoporous zeolitesupport. Contacting of the hierarchical mesoporous zeolite support withthe solution containing the first metal catalyst precursor and thesecond metal catalyst precursor may result in a mixture of amultifunctional catalyst precursor dispersed in the solution. Themixture may also include the remaining first metal catalyst precursor,second metal catalyst precursor, and any other constituents that are notadsorbed onto the outer surfaces and pore surfaces of the zeolitesupport. The multifunctional catalyst precursor may include at least thefirst metal catalyst precursor and the second metal catalyst precursordeposited on or adsorbed onto the outer surfaces or pore surfaces of thehierarchical mesoporous zeolite support.

As previously discussed, after contacting the hierarchical mesoporouszeolite support with the solution comprising the first metal catalystprecursor and the second metal catalyst precursor, the excess liquids,such as solution or solvent, may be removed from the mixture to producea multifunctional catalyst precursor. Removing the liquid components mayinclude removing the excess solution from the multifunctional catalystprecursor and drying the multifunctional catalyst precursor. Removingthe excess solution from the multifunctional catalyst precursor mayinclude subjecting the mixture to decantation, filtration, vacuumfiltration, or combinations of these. In some embodiments, removing theliquids from the mixture may include vacuum filtration of the mixture ata temperature of from 25° C. to 90° C. Drying the multifunctionalcatalyst precursor may include maintaining the multifunctional catalystprecursor at a temperature greater than or equal to the boilingtemperature of the solvent, such as at a temperature of from 90° C. to200° C. Drying may be conducted for a drying period sufficient to removethe solvent to a level of less than 1 wt. % of the total weight of themultifunctional catalyst precursor. The drying period may be from 1 hourto 24 hours, such as from 2 hours to 12 hours. Drying may removeadditional solvent from the multifunctional catalyst through evaporationof the solvent. In some embodiments, the solvent may be water, anddrying may include maintaining the multifunctional catalyst precursor ata temperature of greater than or equal to 100° C. for a drying period ofgreater than or equal to 1 hour.

As previously discussed, the method may further include calcining themultifunctional catalyst precursor to produce the multifunctionalcatalyst of the present disclosure. Calcining the multifunctionalcatalyst precursor may be conducted after removal of the excess solutionand solvent from the multifunctional catalyst precursor. Themultifunctional catalyst precursor may be calcined at a temperature offrom 500° C. to 600° C. and for a calcination period of from 4 hours to6 hours to produce the multifunctional catalyst.

The methods described in this disclosure are based on wet impregnationof the first and second catalyst precursors onto the outer surfaces andpore surfaces of the hierarchical mesoporous zeolite support. It isunderstood that other techniques know in the art may be employed todeposit the heteropolyacids and other metal catalyst precursors onto theouter surfaces and pore surfaces of the hierarchical mesoporous zeolitesupport to prepare the multifunctional catalyst.

The multifunctional catalyst for upgrading pyrolysis oil produced by themethods described in this disclosure may include at least a first metalcatalyst and a second metal catalyst supported on the outer surfaces andpore surfaces of a hierarchical mesoporous zeolite support. The firstmetal catalyst and the second metal catalyst may include any of themetals previous described in this disclosure for the first metalcatalyst and second metal catalyst, respectively. The multifunctionalcatalyst may also include the heteroatom from the heteropolyacid—such asbut not limited to phosphorous, silicon, arsenic, germanium, orcombinations of these—supported on the outer surfaces or pore surfacesof the zeolite support. In some embodiments, the first metal catalystmay be molybdenum and the second metal catalyst may be cobalt orvanadium, where at least the molybdenum is provided by theheteropolyacid. In some embodiments, the cobalt may also be provided bythe same or a different heteropolyacid from the heteropolyacid thatcontributes the molybdenum. In some embodiments, the multifunctionalcatalyst may include molybdenum, cobalt, and phosphorous deposited onthe outer surfaces and pore surfaces of a hierarchical mesoporous betazeolite support, where at least the molybdenum and the phosphorous areprovided by the heteropolyacid. In some embodiments, the multifunctionalcatalyst may include molybdenum, cobalt, and silicon deposited on theouter surfaces and pore surfaces of the hierarchical mesoporous betazeolite support.

The use of a heteropolyacid for at least one of the metal catalystprecursors may reduce the acidity of the multifunctional catalystcompared to commercially available catalysts for upgrading pyrolysis oilprepared using conventional metal catalyst precursors. Themultifunctional catalyst for upgrading pyrolysis oil of the presentdisclosure made using one or more than one heteropolyacid may have anacidity less than an acidity of an existing commercially availablecatalyst having the same metal catalyst species but made withconventional metal catalyst precursors. The multifunctional catalyst mayhave an acidity less than 15,000 micromoles of ammonia per gram(μmol(NH₃)/g), less than or equal to 12,000, less than or equal to10,000 μmol(NH₃)/g, less than or equal to 9,000 μmol(NH₃)/g, or lessthan or equal to 8,000 μmol(NH₃)/g. In some embodiments, themultifunctional catalyst may have an acidity of from 1,000 μmol(NH₃)/gto 15,000 μmol(NH₃)/g, from 1,000 μmol(NH₃)/g to 12,000 μmol(NH₃)/g,from 1,000 μmol(NH₃)/g to 10,000 μmol(NH₃)/g, from 1,000 μmol(NH₃)/g to9,000 μmol(NH₃)/g, or from 1,000 μmol(NH₃)/g to 8,000 μmol(NH₃)/g.

The multifunctional catalyst for upgrading pyrolysis oil of the presentdisclosure may have a BET surface area of greater than or equal to 300meters squared per gram (m²/g). As used herein, “BET surface area”refers to the average surface area of the metallic oxide particles asmeasured by the Brunauer Emmett Teller (BET) nitrogen absorption methodaccording to ASTM D-6556 (American Society for Testing and Materialsmethod D-6556). The multifunctional catalyst for upgrading pyrolysis oilof the present disclosure may have a BET surface area of greater than orequal to 310 m²/g, greater than or equal to 320 m²/g, or even greaterthan or equal to 350 m²/g. The multifunctional catalyst for upgradingpyrolysis oil of the present disclosure may have a BET surface area ofless than or equal to 700 m²/g, less than or equal to 600 m²/g, lessthan or equal to 500 m²/g, or even less than or equal to 400 m²/g. Insome embodiments, the multifunctional catalyst for upgrading pyrolysisoil of the present disclosure may have a BET surface area of from 300m²/g to 700 m²/g, from 300 m²/g to 600 m²/g, from 300 m²/g to 500 m²/g,from 300 m²/g to 400 m²/g, from 310 m²/g to 700 m²/g, from 310 m²/g to600 m²/g, from 310 m²/g to 500 m²/g, from 310 m²/g to 400 m²/g, from 320m²/g to 700 m²/g, from 320 m²/g to 600 m²/g, from 320 m²/g to 500 m²/g,from 320 m²/g to 400 m²/g, from 350 m²/g to 700 m²/g, from 350 m²/g to600 m²/g, from 350 m²/g to 500 m²/g, from 350 m²/g to 400 m²/g, from 400m²/g to 700 m²/g, from 400 m²/g to 600 m²/g, of from 400 m²/g to 500m²/g.

In some embodiments, the multifunctional catalyst for upgradingpyrolysis oil may be a multifunctional catalyst produced by a processthat may include contacting the hierarchical mesoporous zeolite supportwith the solution comprising at least the first metal catalyst precursorand the second metal catalyst precursor. The hierarchical mesoporousmesoporous zeolite support may have an average pore size of from 2 nm to40 nm as determined by BJH analysis. The hierarchical mesoporous zeolitesupport may have any other compositions, features, or characteristicspreviously described in this disclosure. The first metal catalystprecursor, the second metal catalyst precursor, or both, may include aheteropolyacid. Contacting the hierarchical mesoporous zeolite supportwith the solution may cause at least the first metal catalyst precursorand the second catalyst precursor to deposit onto outer surfaces andpore surfaces of the hierarchical mesoporous zeolite support to producea multifunctional catalyst precursor. The solution, the first metalcatalyst precursor, the second metal catalyst precursor, and one or moreheteropolyacids may have any of the compositions, properties, orcharacteristics previously described in this disclosure for each ofthese, respectively. The method may further include removing the excesssolution from the multifunctional catalyst precursor, and calcining themultifunctional catalyst precursor to produce the multifunctionalcatalyst. Each of the contacting step, removing excess solution step,and calcining step may be conducted under any of the process conditionspreviously described in this disclosure in relation to each of theseprocess steps. The multifunctional catalyst produced by this method mayinclude at least a first metal catalyst and a second metal catalystdeposited on the outer surfaces and the pore surfaces of thehierarchical mesoporous zeolite support. The multifunctional catalystproduced by the method may have any of the compositions, properties, orcharacteristics previously described in this disclosure for themultifunctional catalyst.

The multifunctional catalyst prepared by the methods described in thisdisclosure may be used to upgrade pyrolysis oil to produce one or morevaluable aromatic intermediates, such as but not limited to benzene,toluene, ethylbenzene, xylenes, other aromatic compounds, orcombinations of these. In some embodiments, a method for upgradingpyrolysis oil may include contacting the pyrolysis oil with themultifunctional catalyst at mild reaction conditions comprising reactiontemperatures of less than 500° C. and pressures less than 6 MPa. Thepyrolysis oil may have any of the compositions or characteristicspreviously described in this disclosure for pyrolysis oil. In someembodiments, the pyrolysis oil may include multi-ring aromaticcompounds. The multifunctional catalyst may be prepared by any of themethods or processes for making the multifunctional catalyst describedin this disclosure and may have any properties, compositions, orattributes described in this disclosure for the multifunctionalcatalyst. In some embodiments, the multifunctional catalyst may beproduced by the process that includes contacting the hierarchicalmesoporous zeolite support with the solution comprising at least thefirst metal catalyst precursor and the second metal catalyst precursor,the first metal catalyst precursor, the second metal catalyst precursor,or both, including a heteropolyacid. The hierarchical mesoporous zeolitesupport may have an average pore size of from 2 nm to 40 nm. Thehierarchical mesoporous zeolite support, the solution, the first metalcatalyst precursor, the second metal catalyst precursor, and one or moreheteropolyacids may have any of the compositions, properties, orcharacteristics previously described in this disclosure for each ofthese, respectively. The contacting may cause at least the first metalcatalyst precursor and the second catalyst precursor to deposit or beadsorbed onto the outer surfaces and pore surfaces of the hierarchicalmesoporous zeolite support to produce a multifunctional catalystprecursor. The process for producing the multifunctional catalyst mayinclude removing excess solution from the multifunctional catalystprecursor, and calcining the multifunctional catalyst precursor toproduce the multifunctional catalyst. Each of the contacting step,removing excess solution step, and calcining step may be conducted underany of the process conditions previously described in this disclosure inrelation to each of these process steps. The multifunctional catalystmay include a first metal catalyst and a second metal catalyst supportedon the hierarchical mesoporous zeolite support.

Contact of the pyrolysis oil with the multifunctional catalyst at thereaction conditions may convert at least a portion of the multi-ringaromatic compounds in the pyrolysis oil to one or more C6-C8 aromaticcompounds. The at least a portion of the multi-ring aromatic compoundsconverted to one or more C6-C8 compounds may include at least 30%, atleast 40%, at least 50%, at least 60%, at least 70%, or at least 80% ofthe multi-ring aromatic compounds in the pyrolysis oil. The C6-C8aromatic compounds may include, but are not limited to, one or more ofbenzene, toluene, ethylbenzene, xylene, or combinations of these. Insome embodiments, contacting the pyrolysis oil with the multifunctionalcatalyst at the reactions conditions may convert the at least a portionof the multi-ring aromatic compounds in the pyrolysis oil to C6-C8aromatic compounds in a single step, without conducting a subsequentchemical reaction step.

Contacting of the pyrolysis oil with the multifunctional catalyst may beconducted at a reaction temperature in a range comparable to thereaction temperatures for processes for upgrading pyrolysis oil usingcommercially-available catalysts prepared using conventional metalcatalyst precursors. In some embodiments, the pyrolysis oil may becontacted with the multifunctional catalyst at a reaction temperature ofless than or equal to 500° C., less than or equal to 450° C., or evenless than or equal to 400° C. The pyrolysis oil may be contacted withthe multifunctional catalyst at a reaction temperature of greater thanor equal to 350° C., greater than or equal to 380° C. or even greaterthan or equal to 400° C. In some embodiments, pyrolysis oil may becontacted with the multifunctional catalyst at a reaction temperature offrom 350° C. to 500° C., from 350° C. to 450° C., from 350° C. to 400°C., from 380° C. to 500° C., from 380° C. to 450° C., from 380° C. to400° C., from 400° C. to 500° C., or from 400° C. to 425° C.

Contacting of the pyrolysis oil with the multifunctional catalyst may beconducted at a reaction pressure less than the reactions pressuresnecessary for upgrading pyrolysis oil using the commercially-availablecatalysts prepared using conventional metal catalyst precursors.Contacting of the pyrolysis oil with the multifunctional catalyst of thepresent disclosure may be conducted at a pressure that is 3 MPa to 5 MPaless than the reaction pressure required to upgrade pyrolysis oil usinga conventional multi-metal catalyst. In some embodiments, the pyrolysisoil may be contacted with the multifunctional catalyst at a reactionpressure less than 6 MPa, less than or equal to 5 MPa, or even less thanor equal to 4 MPa. In some embodiments, the pyrolysis oil may becontacted with the multifunctional catalyst at a reaction pressuregreater than or equal to 0.1 MPa, greater than or equal to 1 MPa, oreven greater than or equal to 2 MPa. In some embodiments, the pyrolysisoil may be contacted with the multifunctional catalyst at a reactionpressure of from 0.1 MPa to 5 MPa, from 0.1 MPa to 4 MPa, from 1 MPa to5 MPa, from 1 MPa to 4 MPa, from 2 MPa to 5 MPa, or even from 2 MPa to 4MPa.

In some embodiments, the method of upgrading pyrolysis oil may furtherinclude separating an upgraded pyrolysis oil from the multifunctionalcatalyst. Separating the upgraded pyrolysis oil from the multifunctionalcatalyst may be conducted using any known method or process ofseparating a fluid from a particulate solid.

Upgrading pyrolysis oil by contacting with the multifunctional catalystof the present disclosure prepared from a hierarchical mesoporouszeolite support and including at least one metal catalyst derived from aheteropolyacid catalyst precursor may produce a greater yield of C6-C8aromatic compounds, such as one or more than one of benzene, toluene,ethylbenzene, xylenes, or combinations of these, compared to upgradingthe pyrolysis oil by contacting with commercially-available catalystsprepared using conventional metal catalyst precursors and microporouscatalyst supports. In some embodiments, upgrading pyrolysis oil bycontacting the pyrolysis oil with the multifunctional catalyst of thepresent disclosure prepared from a hierarchical mesoporous zeolitesupport using heteropolyacids may produce a combined yield of C6-C8aromatic compounds of greater than or equal to 40 wt. %, greater than orequal to 45 wt. %, or even greater than or equal to 50 wt. %, based onthe total weight of the upgraded pyrolysis oil separated from themultifunctional catalyst. Upgrading pyrolysis oil by contacting thepyrolysis oil with the multifunctional catalyst of the presentdisclosure prepared from a hierarchical mesoporous zeolite support usingheteropolyacids may produce a combined yield of C6-C8 aromatic compoundsthat is at least 50% greater, at least 80% greater, or even at least100% greater than a combined yield of C6-C8 aromatic compounds producedby contacting the pyrolysis oil with a multi-metal catalyst preparedfrom microporous catalyst supports and conventional metal catalystprecursors at the same temperature, pressure, and flow rates.

EXAMPLES

The following examples illustrate the methods of the present disclosurefor producing multifunctional catalysts for upgrading pyrolysis oil andthe methods for upgrading pyrolysis oil using the multifunctionalcatalysts. The Examples are not intended to limit the scope of thepresent disclosure in any way, in particular with respect to specificmass flow rates, stream compositions, temperatures, pressures, time onstream, amounts of catalytic metals on the zeolite support, or othervariables fixed for the purposes of conducting the experiments.

Comparative Example 1: Comparative Catalyst for Upgrading Pyrolysis Oil

For Comparative Example 1, a comparative catalyst comprising a firstcatalyst metal and second catalyst metal deposited on the outer surfacesand pore surfaces of a nano-beta zeolite support was prepared usingconventional metal precursors and no heteropolyacids. The first metalcatalyst precursor was ammonium molybdate tetrahydrate having chemicalformula [(NH₃)₆Mo₇O₂₄.4H₂O], which was obtained from Sigma-Aldrich. Thesecond metal catalyst precursor was cobalt (II) nitrate hexahydratehaving chemical formula [Co(NO₃)₂.6H₂O], which was also obtained fromSigma-Aldrich. The nano-beta zeolite catalyst support for ComparativeExample 1 was CP814E nano-beta zeolite obtained from ZeolystInternational. The nano-beta zeolite support particles had a ratio ofthe molar amount of silica (SiO₂) divided by the molar amount of alumina(Al₂O₃) of 25 (Beta-N).

The comparative catalyst of Comparative Example 1 was produced by adding10 grams of the nano-beta zeolite catalyst support (Beta-N) to a roundbottom flask. A Solution A was prepared by dissolving 3.08 grams of[(NH₃)₆Mo₇O₂₄.4H₂O] in 50 milliliters (mL) of distilled water. ASolution B was then prepared by dissolving 2.65 grams of the[Co(NO₃)₂.6H₂O] in 50 mL of distilled water. The amounts of[(NH₃)₆Mo₇O₂₄.4H₂O] and [Co(NO₃)₂.6H₂O] were selected to provide a finalmetal loading in the comparative catalyst of Comparative Example 1 of 3wt. % Co and 12 wt. % Mo, respectively. Solution A and Solution B werethen mixed together and added to Beta-N support in the round bottomflask. The combined solution and the Beta-N support were mixed for 2hours. The water was removed from the Beta-N support impregnated withthe first and second metal catalyst precursors under vacuum at atemperature of 50° C., and the solid sample was dried overnight at atemperature of 100° C. The solid sample was then calcined at atemperature of 500° C. for five hours to obtain the comparative catalystof Comparative Example 1.

Comparative Example 2: Comparative Phosphorous-Containing Catalyst forUpgrading Pyrolysis Oil

For Comparative Example 2, a comparative phosphorous-containing catalystcomprising a first catalyst metal, second catalyst metal, andphosphorous deposited on the outer surfaces and pore surfaces of theBeta-N support was prepared using conventional metal precursors and noheteropolyacids. The first metal catalyst precursor was ammoniummolybdate tetrahydrate having chemical formula [(NH₃)₆Mo₇O₂₄.4H₂O],which was obtained from Sigma-Aldrich. The second metal catalystprecursor was cobalt (II) nitrate hexahydrate having chemical formula[Co(NO₃)₂.6H₂O], which was also obtained from Sigma-Aldrich. The Beta-Nsupport was the nano-beta zeolite catalyst support previously describedin Comparative Example 1. Phosphoric acid (H₃PO₄) obtained fromSigma-Aldrich was used to incorporate the phosphorous.

The comparative phosphorous-containing catalyst of Comparative Example 2was produced by adding 10 grams of the Beta-N support to a round bottomflask. A Solution A was prepared by dissolving 3.08 grams of the firstmetal catalyst precursor [(NH₃)₆Mo₇O₂₄.4H₂O] in 50 milliliters (mL) ofdistilled water. A Solution B was then prepared by dissolving 2.65 gramsof the second metal catalyst precursor [Co(NO₃)₂.6H₂O] in 50 mL ofdistilled water. The amounts of [(NH₃)₆Mo₇O₂₄.4H₂O] and [Co(NO₃)₂.6H₂O]were selected to provide a final metal loading in the comparativecatalyst of Comparative Example 2 of 3 wt. % Co and 12 wt. % Mo,respectively. Solution A and Solution B were then mixed together, and0.15 grams of phosphoric acid was dissolved in the combined solution toproduce Solution C. Solution C was then added to the Beta-N support inthe round bottom flask and mixed for 2 hours. The water was removed fromthe Beta-N support impregnated with the first and second metal catalystprecursors under vacuum at a temperature of 50° C., and the solid samplewas dried overnight at a temperature of 100° C. The solid sample wasthen calcined at a temperature of 500° C. for five hours to obtain thecomparative phosphorous-containing catalyst of Comparative Example 2.

Example 3: Multifunctional Catalyst for Upgrading Pyrolysis Oil PreparedUsing a Heteropolyacid

In Example 3, a multifunctional catalyst comprising a first metalcatalyst, a second metal catalyst, and phosphorous deposited on theouter surfaces and pore surfaces of the Beta-N support was preparedusing a heteropolyacid for first metal catalyst precursor and thephosphorous. The first metal catalyst precursor was phosphormolybdicheteropolyacid having chemical formula [H₃PMo₁₂O₄₀], which was obtainedfrom Sigma-Aldrich. The second metal catalyst precursor was cobalt (II)nitrate hexahydrate having chemical formula [Co(NO₃)₂.6H₂O], which wasalso obtained from Sigma-Aldrich. The Beta-N support was the nano-betazeolite catalyst support previously described in Comparative Example 1.

The multifunctional catalyst of Example 3 was produced by adding 10grams of the Beta-N support to a round bottom flask. Solution A wasprepared by dissolving 2.89 grams of the heteropolyacid of the firstmetal catalyst precursor [H₃PMo₁₂O₄₀] in 50 milliliters (mL) ofdistilled water. Solution B was then prepared by dissolving 2.24 gramsof the second metal catalyst precursor [Co(NO₃)₂.6H₂O] in 50 mL ofdistilled water. The amounts of the first metal catalyst precursor andsecond metal catalyst precursor were calculated to provide the samemetal loading as the comparative catalysts of Comparative Examples 1 and2 (3 wt. % Co and 12 wt. % Mo). Solution A and Solution B were thenmixed together and added to the Beta-N support in the round bottomflask. The combined solution and the Beta-N support were mixed for 2hours. The water was removed from the Beta-N support impregnated withthe first and second metal catalyst precursors under vacuum at atemperature of 50° C., and the resulting multifunctional catalystprecursor was dried overnight at a temperature of 100° C. The driedmultifunctional catalyst precursor was then calcined at a temperature of500° C. for five hours to obtain the multifunctional catalyst of Example3.

Example 4: Multifunctional Catalyst for Upgrading Pyrolysis Oil PreparedUsing a Hierarchical Mesoporous Beta Zeolite Support

In Example 4, the multifunctional catalyst for upgrading pyrolysis oilwas prepared by first upgrading the zeolite support to a hierarchicalmesoporous zeolite support. The first metal catalyst, second metalcatalyst, and phosphorous were then deposited on the outer surfaces andpore surface of the hierarchical mesoporous zeolite support using aheteropolyacid for the first metal catalyst precursor and phosphorous.

The starting beta zeolite was HSZ-931 HOA beta zeolite obtained fromTosoh, which is a micrometer-sized beta zeolite having a molar ratio ofsilica to alumina (SiO₂/Al₂O₃) of 28. The beta zeolite was converted tohierarchical mesoporous beta zeolite by adding 22.2 grams of the HSZ-931HOA beta zeolite to 600 mL of a 0.2 molar (M) solution of NaOH. Themixture was then subjected to hydrothermal desilication at a temperatureof 150° C. for 21 hours. The hierarchical mesoporous beta zeolite had afinal molar ratio of silica to alumina after the conversion of 20. Thehierarchical mesoporous beta zeolite had an average pore size of 10 nmwith a peak pore size in the range of 20-25 nm, as determined by themethods previously discussed in this disclosure. The hierarchicalmesoporous beta zeolite also had a pore volume of 0.59 cubic centimetersper gram.

The acidity of the hierarchical mesoporous beta zeolite was adjusted bydealumination in a diluted nitric acid solution. In particular, forExample 4, the hierarchical mesoporous beta zeolite was dealimunated bycontacting the hierarchical mesoporous beta zeolite with a 0.2 Msolution of nitric acid (HNO₃) at 80° C. for a period of 2 hours. Thedealuminated hierarchical mesoporous beta zeolite was then ion-exchangedin a 0.8 M solution of ammonium nitrate (NH₄NO₃) for 2 hours at 80° C.one time. The ion-exchanged dealuminated hierarchical mesoporous betazeolite was then dried and calcined at 550° C. for 5 hours to producethe hierarchical mesoporous beta zeolite support of Example 4, which isreferred to in this disclosure as Beta-M50 zeolite support.

The multifunctional catalyst of Example 4 was then produced by adding 5grams of the Beta-M50 zeolite support to a round bottom flask. SolutionA was prepared by dissolving 1.44 grams of the heteropolyacid of thefirst metal catalyst precursor [H₃PMo₁₂O₄₀] in 15 mL of distilled water.Solution B was then prepared by dissolving 1.12 grams of the secondmetal catalyst precursor [Co(NO₃)₂.6H₂O] in 15 mL of distilled water.The amounts of the first metal catalyst precursor and second metalcatalyst precursor were calculated to provide the same metal loading asthe comparative catalysts of Comparative Examples 1 and 2 and themultifunctional catalyst of Example 3 (3 wt. % Co and 12 wt. % Mo).Solution A and Solution B were then mixed together and added to theBeta-M50 zeolite support in the round bottom flask. The combinedsolution and the Beta-M50 zeolite support were mixed for 2 hours. Thewater was removed from the Beta-M50 zeolite support impregnated with thefirst and second metal catalyst precursors under vacuum at a temperatureof 50° C., and the resulting multifunctional catalyst precursor wasdried overnight at a temperature of 100° C. The dried multifunctionalcatalyst precursor was then calcined at a temperature of 500° C. forfive hours to obtain the multifunctional catalyst of Example 4.

Example 5: Upgrading Pyrolysis Oil

In Example 5, the comparative catalysts of Comparative Examples 1 and 2and the multifunctional catalyst of Examples 3 and 4 were used toupgrade a model pyrolysis oil composition to produce at least benzene,toluene, ethylbenzene, and xylene. 1-methylnaphthalene obtained fromSigma-Aldrich was used as the model pyrolysis oil.

Referring to FIG. 3, the apparatus 100 in which the model pyrolysis oilupgrading was conducted is schematically depicted. The apparatus 100included a fixed bed reactor 110 with the catalyst loaded in zone 111.The fixed bed reactor 110 was maintained in a hot box 112 to maintainthe fixed bed reactor 110 at constant temperature. The liquid feed 116,which included the model pyrolysis oil (1-methylnaphthalene) wasintroduced to the fixed bed reactor 110 using a liquid pump 120.Hydrogen 118 and nitrogen 119 can also be added to the liquid feed 116upstream of the fixed bed reactor 110. The liquid feed 116 was passedthrough a heat exchanger 130 to adjust a temperature of the liquid feed116 before passing it to the fixed bed reactor 110. The liquid feed 116was contacted with the catalyst in the fixed bed reactor 110, thecontacting causing reaction of at least the model pyrolysis oil(1-methylnaphthalene) to upgrade the model pyrolysis oil to produce aliquid product stream 114 comprising at least benzene, toluene,ethylbenzene, and xylene. The operating conditions of the fixed bedreactor 110 are listed in Table 1.

The liquid product stream 114 was passed from the fixed bed reactor 110to a liquid gas separator 140, in which the liquid product stream 114was separated into a gaseous fraction 142 comprising the lesser boilingtemperature constituents and a liquid fraction 144 comprising thegreater boiling point fractions and unreacted model pyrolysis oil(1-methylnaphthalene). The liquid fraction 144 was analyzed forcomposition. The gaseous fraction 142 was passed to an online gaschromatograph for analysis of the composition of the gaseous fraction142. The compositions of the gaseous fraction 142 and liquid fraction144 were then used to determine the yield for each of the constituentsof the liquid product stream 114. The yields for each of the compoundsproduced in the fixed bed reactor for each of the catalysts ofComparative Examples 1 and 2 and Examples 3 and 4 are providedsubsequently in Table 1. The yields for each of the constituents inTable 1 are provided in weight percent based on the total mass flow rateof the liquid product stream 114.

TABLE 1 Results of Upgrading of Model Pyrolysis Oil with the ComparativeCatalysts of Comparative Examples 1 and 2 and the MultifunctionalCatalysts of Examples 3 and 4 Comparative Comparative Example 1 Example2 Example 3 Example 4 Catalyst Support Nano-beta Nano-beta Nano-betaBeta-M50 zeolite zeolite zeolite First Metal Catalyst (NH₃)₆Mo₇O₂₄•4H₂O(NH₃)₆Mo₇O₂₄•4H₂O H₃PMo₁₂O₄₀ H₃PMo₁₂O₄₀ Precursor Second Metal CatalystCo(NO₃)₂•6H₂O Co(NO₃)₂•6H₂O Co(NO₃)₂•6H₂O Co(NO₃)₂•6H₂O PrecursorPhosphorous Source N/A H₃PO₄ H₃PMo₁₂O₄₀ H₃PMo₁₂O₄₀ Catalyst Acidity4703.6 14570.0 3258.8 8786.1 (μmol(NH₃)/g) Catalyst BET Surface 329.104320.730 350.632 368.521 Area (m²/g) Reaction Temperature 400 400 400 400(° C.) Weight Hourly Space 1.2 1.2 1.2 1.2 Velocity (hour⁻¹) TotalPressure (MPa) 3 3 3 3 Total Conversion of 86.1 81.8 86.7 94.31-methylnaphthalene (%) Time on Stream (hour) 20 20 20 20 Benzene Yield(wt. %) 4.60 4.36 6.25 10.24 Toluene Yield (wt. %) 12.96 11.75 17.6426.59 Ethylbenzene Yield 2.47 2.22 3.71 4.37 (wt. %) Total Xylene Yield7.30 5.68 9.27 16.80 (wt. %) Para-Xylene Yield 1.78 1.40 2.28 4.02 (wt.%) Meta-Xylene Yield 3.83 2.99 4.86 8.97 (wt. %) Ortho-Xylene Yield 1.691.29 2.13 3.81 (wt. %) C(3-4)-Benzene* Yield 15.02 9.09 14.44 15.36 (wt.%) Tetralin Yield (wt. %) 0.60 0.23 0.34 0.17 Naphthalene Yield 2.532.31 2.92 2.05 (wt. %) Methyltetralin Yield 12.91 23.61 19.71 11.28 (wt.%) Other 2-Ar (wt. %) 8.89 7.32 7.36 3.82 Total BTEX Yield** 27.3 24.036.7 58.0 (wt. %) *C(3-4)-Benzene refers to benzene substituted with oneor more alkyl group for which the total number of carbon atoms in thealkyl group is 3 or 4. **Total BTEX Yield refers to the total combinedyield of benzene, toluene, ethylbenzene, and xylenes (para-xylene,meto-xylene, and ortho-xylene).

As shown in Table 1, the multifunctional catalyst of Example 4 providedthe best performance for upgrading the model pyrolysis oil(1-methylnaphthalene) to benzene, toluene, ethylbenzene, and xylenes(BTEX). The total BTEX yield obtained using the multifunctional catalystof Example 4 was 58 wt. %, which is greater than 2 times the yield ofBTEX obtained with the comparative catalysts of Comparative Examples 1and 2, which comprise catalyst made with conventional metal catalystprecursors deposited on a nano-beta zeolite support. The multifunctionalcatalyst of Example 4 prepared using the Beta-M50 hierarchicalmesoporous beta zeolite support resulted in a 58% increase in the totalyield of BTEX compared to the multifunctional catalyst of Example 3,which was prepared using a heteropolyacid but included the nano-betazeolite support. The multifunctional catalyst of Example 4 also resultedin the greatest overall conversion of 1-methylnaphthalene at 94.3%conversion. Thus, at the same temperature and pressure, themultifunctional catalyst of Example 4 that includes a hierarchicalmesoporous beta zeolite support may provide greater yield of BTEXcompared to conventional catalysts such as the comparative catalysts ofComparative Examples 1 and 2.

Example 6: Effect of Acidity of Hierarchical Mesoporous Zeolite onPerformance of the Multifunctional Catalyst

In Example 6, the effects of changing the acidity of the hierarchicalmesoporous beta zeolite support on the performance of themultifunctional catalysts were studied. For Example 6, the starting betazeolite was the HSZ-931 HOA beta zeolite obtained from Tosoh, which is amicrometer-sized beta zeolite having a molar ratio of silica to alumina(SiO₂/Al₂O₃) of 28. The beta zeolite was converted to hierarchicalmesoporous beta zeolite by adding 22.2 grams of the HSZ-931 HOA betazeolite to 600 mL of a 0.2 molar (M) solution of NaOH. The mixture wasthen subjected to hydrothermal desilication at a temperature of 150° C.for 21 hours. The hierarchical mesoporous beta zeolite had a final molarratio of silica to alumina after the conversion of 20. The hierarchicalmesoporous beta zeolite had an average pore size of 10 nm with a peakpore size in the range of 20-25 nm, as determined by the methodspreviously discussed in this disclosure. The hierarchical mesoporousbeta zeolite also had a pore volume of 0.59 cubic centimeters per gram.

For Sample 6A, the acidity was not adjusted. Instead, the hierarchicalmesoporous beta zeolite of Sample 6A was subjected to ion-exchange in a0.8 M solution of NH₄NO₃ for 2 hours at 80° C. three times, dried, andcalcined at 550° C. for 5 hours. The hierarchical mesoporous betazeolite support of Sample 6A is referred to in this disclosure asBeta-M20 zeolite support.

For Samples 6B, 6C, and 6D, the acidity of the hierarchical mesoporousbeta zeolite was adjusted by dealumination in a diluted nitric acidsolution. For each of Samples 6B, 6C, and 6D, the hierarchicalmesoporous beta zeolite was dealimunated by contacting the hierarchicalmesoporous beta zeolite with a solution of nitric acid (HNO₃) at 80° C.for a period of 2 hours. The concentrations of HNO₃ in the solutionswere 0.15 M, 0.2 M, and 0.25 M for Samples 6B, 6C, and 6D, respectively.Each of the dealuminated hierarchical mesoporous beta zeolites ofSamples 6B, 6C, and 6D were then ion-exchanged in a 0.8 M solution ofNH₄NO₃ for 2 hours at 80° C. one time. The ion-exchanged dealuminatedhierarchical mesoporous beta zeolite were then dried and calcined at550° C. for 5 hours to produce the hierarchical mesoporous beta zeolitesupport of Samples 6B, 6C, and 6D, which are referred to in thisdisclosure as Beta-M35, Beta-M50, and Beta-M66, respectively.

The hierarchical mesoporous beta zeolite supports of Samples 6A, 6B, 6C,and 6D were evaluated for average pore size (average diameter), BETsurface area (S_(BET)), external surface area (S_(ext)), microporevolume (V_(mic)), total pore volume (V_(T)), total acidity, and maximumdesorption temperature (T_(max)), which are provided subsequently inTable 2. The external surface area (S_(ext)) was determined using thet-plot method, which is well-known in the art. The micropore volume(V_(mic)) and total pore volume (V_(T)) were determined by the NLDFTmethod previously discussed in this disclosure.

TABLE 2 Properties of Hierarchical Mesoporous Beta Zeolite Supports forExample 6 Sample 6A 6B 6C 6D Silica/Alumina 20 35 50 66 Ratio Averagepore 9.9 9.8 9.9 10.3 size (nm) S_(BET) (m²/g) 611 611 608 609 S_(ext)(m²/g) 197 205 197 196 V_(mic) (cm³/g) 0.28 0.28 0.27 0.27 V_(T) (cm³/g)0.58 0.59 0.59 0.60 Total Acidity 0.79 0.70 0.54 0.36 (mmol/g) T_(max)(° C.) 313 ± 2 340 ± 5 347 ± 3 330 ± 3

The multifunctional catalysts of Example 6 (Catalysts 6A-6D) wereprepared from the Beta-M20, Beta-M35, Beta-M50, and Beta-M66 zeolitesupports using the heteropolyacid according to the method previouslydescribed in Example 4. The multifunctional catalysts of Example 6 werethen used to upgrade a model pyrolysis oil using the apparatus andmethods previously described in Example 5. The yields of each of thecompounds produced in the fixed bed reactor for each of the catalysts ofExample 6 are provided in Table 3. The yields for each of theconstituents in Table 3 are provided in weight percent based on thetotal mass flow rate of the liquid product stream.

TABLE 3 Results of Upgrading of Model Pyrolysis Oil with the Catalystsof Example 6 6A 6B 6C 6D Catalyst Support Beta-M20 Beta-M35 Beta-M50Beta-M66 First Metal Catalyst H₃PMo₁₂O₄₀ H₃PMo₁₂O₄₀ H₃PMo₁₂O₄₀H₃PMo₁₂O₄₀ Precursor Second Metal Catalyst Co(NO₃)₂•6H₂O Co(NO₃)₂•6H₂OCo(NO₃)₂•6H₂O Co(NO₃)₂•6H₂O Precursor Phosphorous Source H₃PMo₁₂O₄₀H₃PMo₁₂O₄₀ H₃PMo₁₂O₄₀ H₃PMo₁₂O₄₀ Catalyst Acidity 10252.8 9438.0 8786.17879.1 (μmol(NH₃)/g) Catalyst BET Surface 357.144 353.125 368.521317.013 Area (m²/g) Reaction Temperature 400 400 400 400 (° C.) WeightHourly Space 1.2 1.2 1.2 1.2 Velocity (hour⁻¹) Total Pressure (MPa) 3 33 3 Total Conversion of 79.9 92.2 94.3 94.5 1-methylnaphthalene (%) Timeon Stream (hour) 20 20 20 20 Benzene Yield (wt. %) 7.90 10.18 10.24 9.93Toluene Yield (wt. %) 20.45 25.47 26.59 26.24 Ethylbenzene Yield 3.394.27 4.37 4.73 (wt. %) Total Xylene Yield 11.99 16.05 16.80 15.64 (wt.%) Para-Xylene Yield 2.89 3.84 4.02 3.79 (wt. %) Meta-Xylene Yield 6.398.60 8.97 8.31 (wt. %) Ortho-Xylene Yield 2.71 3.61 3.81 3.54 (wt. %)C(3-4)-Benzene* Yield 12.18 13.91 15.36 17.07 (wt. %) Tetralin Yield(wt. %) 0.22 0.16 0.17 0.27 Naphthalene Yield 1.91 1.63 2.05 2.44 (wt.%) Methyltetralin Yield 11.89 9.74 11.28 11.37 (wt. %) Other 2-Ar (wt.%) 4.58 3.26 3.82 5.14 Total BTEX Yield** 43.7 56.0 58.0 56.5 (wt. %)*C(3-4)-Benzene refers to benzene substituted with one or more alkylgroup, for whichthe total number of carbon atoms in the alkyl group is 3or 4. **Total BTEX Yield refers to the total combined yield of benzene,toluene, ethylbenzene, and xylenes (para-xylene, meta-xylene, andortho-xylene).

As shown in Table 3, the inclusion of the hierarchical mesoporous betazeolite support produces a combined yield of BTEX of at least 40 wt. %regardless of the ratio of silica to alumina (SiO₂/Al₂O₃) in thehierarchical mesoporous beta zeolite support, for SiO₂/Al₂O₃ betweenabout 20 and about 66 (Beta-M20 and Beta-M66). However, when theproportion of alumina is decreased so that the ratio SiO₂/Al₂O₃ is atleast about 35, the combined yield of BTEX produced through contact ofthe multifunctional catalyst with the pyrolysis oil increases to 56 wt.%. The combined yield of BTEX is greatest for Sample 6C, for which thehierarchical mesoporous beta zeolite support was Beta-M50 having aSiO₂/Al₂O₃ of about 50. At a SiO₂/Al₂O₃ of 66 in Sample 6D, the combinedyield of BTEX decreases again to 56 wt. %. This indicates that removalof too much alumina (for example, at a SiO₂/Al₂O₃ greater than 66) maylead to reduced activity of the multifunctional catalyst for upgradingpyrolysis oil to BTEX.

In a first aspect of the present disclosure, a method of making amultifunctional catalyst for upgrading pyrolysis oil can includecontacting a hierarchical mesoporous zeolite support with a solutioncomprising at least a first metal catalyst precursor and a second metalcatalyst precursor. The hierarchical mesoporous zeolite support may havean average pore size of from 2 nanometers to 40 nanometers as determinedby Barrett-Joyner-Halenda (BJH) analysis, the first metal catalystprecursor, the second metal catalyst precursor, or both, comprises aheteropolyacid, and the contacting deposits the first metal catalystprecursor and the second catalyst precursor onto outer surfaces and poresurfaces of the hierarchical mesoporous zeolite support to produce amultifunctional catalyst precursor. The method may further includeremoving excess solution from the multifunctional catalyst precursor andcalcining the multifunctional catalyst precursor to produce themultifunctional catalyst comprising at least a first metal catalyst anda second metal catalyst deposited on the outer surfaces and poresurfaces of the hierarchical mesoporous zeolite support.

A second aspect of the present disclosure is directed to amultifunctional catalyst for upgrading pyrolysis oil, where themultifunctional catalyst is produced by a process that includescontacting a hierarchical mesoporous zeolite support with a solutioncomprising at least a first metal catalyst precursor and a second metalcatalyst precursor. The hierarchical mesoporous zeolite support may havean average pore size of from 2 nanometers to 40 nanometers as determinedby Barrett-Joyner-Halenda (BJH) analysis, the first metal catalystprecursor, the second metal catalyst precursor, or both, comprises aheteropolyacid, and the contacting deposits the first metal catalystprecursor and the second catalyst precursor onto outer surfaces and poresurfaces of the hierarchical mesoporous zeolite support to produce amultifunctional catalyst precursor. The process may further includeremoving excess solution from the multifunctional catalyst precursor andcalcining the multifunctional catalyst precursor to produce themultifunctional catalyst. The multifunctional catalyst may include atleast a first metal catalyst and a second metal catalyst deposited onthe outer surfaces and the pore surfaces of the zeolite support.

A third aspect of the present disclosure may include either of the firstor second aspects, in which the hierarchical mesoporous zeolite supportcomprises a hierarchical mesoporous beta zeolite support.

A fourth aspect of the present disclosure may include any of the firstthrough third aspects, in which the hierarchical mesoporous zeolitesupport has an average pore size of from 5 nanometers to 25 nanometersas determined by BJH analysis.

A fifth aspect of the present disclosure may include any of the firstthrough fourth aspects, in which the hierarchical mesoporous zeolitesupport has a total pore volume of greater than or equal to 0.35 cubiccentimeters per gram.

A sixth aspect of the present disclosure may include any of the firstthrough fifth aspects, in which the hierarchical mesoporous zeolitesupport comprises a molar ratio of silica to alumina of from 20 to 100.

A seventh aspect of the present disclosure may include any of the firstthrough sixth aspects, in which the method or process further comprisesproducing the hierarchical mesoporous zeolite support.

An eighth aspect of the present disclosure may include the seventhaspect, in which producing the hierarchical mesoporous zeolite supportmay comprise converting a microporous parent zeolite into thehierarchical mesoporous zeolite support through desilication of themicroporous parent zeolite.

A ninth aspect of the present disclosure may include the eighth aspect,in which desilication of the microporous parent zeolite to produce thehierarchical mesoporous zeolite support may include mixing themicroporous zeolite with an aqueous metal hydroxide solution and heatingthe microporous zeolite and aqueous metal hydroxide mixture to atemperature of greater than or equal to 100 degrees Celsius to producethe hierarchical mesoporous zeolite support.

A tenth aspect of the present disclosure may include any of the firstthrough ninth aspects, in which the heteropolyacid may include at leastone metal selected from cobalt, molybdenum, vanadium, or combinations ofthese metals and at least one heteroatom selected from phosphorous,silicon, arsenic, or combinations of these heteroatoms.

An eleventh aspect of the present disclosure may include any of thefirst through tenth aspects, in which the first metal catalyst precursorcomprises the heteropolyacid.

A twelfth aspect of the present disclosure may include any of the firstthrough eleventh aspects, in which the first metal catalyst precursorcomprises a first heteropolyacid and the second metal catalyst precursorcomprises a second heteropolyacid that is different from the firstheteropolyacid.

A thirteenth aspect of the present disclosure may include the twelfthaspect, in which the first heteropolyacid or the second heteropolyacidis H₃PMo₁₂O₄₀.

A fourteenth aspect of the present disclosure may include any of thefirst through eleventh aspects, in which the heteropolyacid comprisesphosphormolybdic heteropolyacid having formula H₃PMo₁₂O₄₀.

A fifteenth aspect of the present disclosure may include any of thefirst through eleventh aspects, in which the first metal catalystprecursor and the second metal catalyst precursor are the sameheteropolyacid, and the heteropolyacid comprises a first metal, a secondmetal that is different from the first metal, and at least oneheteroatom.

A sixteenth aspect of the present disclosure may include the fifteenthaspect, in which the heteropolyacid comprises decamolybdodicobaltateheteropolyacid having chemical formula H₆[Co₂Mo₁₀O₃₈H₄].

A seventeenth aspect of the present disclosure may include any of thefirst through sixteenth aspects, in which the multifunctional catalystprecursor is calcined at a temperature of 400 degrees Celsius to 700degrees Celsius and for a time of from 4 hours to 6 hours to produce themultifunctional catalyst.

An eighteenth aspect of the present disclosure may include any of thefirst through seventeenth aspects, in which removing the excess solutionfrom the multifunctional catalyst precursor comprises filtering ordecanting the excess solution from the multifunctional catalystprecursor and drying the multifunctional catalyst precursor to removesolvent.

A nineteenth aspect of the present disclosure may include any of thefirst through eighteenth aspects, in which the first metal catalystcomprises molybdenum and the second metal catalyst comprises cobalt,where at least the heteropolyacid includes the molybdenum.

A twentieth aspect of the present disclosure may be directed to themultifunctional catalyst produced by the methods and processes of any ofthe first through nineteenth aspects.

A twenty-first aspect of the present disclosure may be directed to amultifunctional catalyst for upgrading pyrolysis oil, themultifunctional catalyst comprising one or more cobalt compounds, one ormore molybdenum compounds, and phosphorous supported on a hierarchicalmesoporous zeolite support. At least one of the molybdenum compounds,cobalt compounds, or phosphorous may be provided by a heteropolyacidprecursor, and the hierarchical mesoporous zeolite support may have anaverage pore size of from 2 nanometers to 40 nanometers as determined byBJH analysis.

A twenty-second aspect of the present disclosure may include any of thefirst through twenty-first aspects, in which the first metal catalyst isthe heteropolyacid and comprises molybdenum and the second metalcatalyst comprises cobalt.

A twenty-third aspect of the present disclosure may include any of thefirst through twenty-second aspects, in which the multifunctionalcatalyst comprises phosphorous deposited on the outer surfaces and poresurfaces of the hierarchical mesoporous zeolite support.

A twenty-fourth aspect of the present disclosure may include any of thefirst through twenty-third aspects, where the multifunctional catalysthas an acidity of less than 15,000 micromoles of ammonia per gram(μmol(NH₃)/g).

A twenty-fifth aspect of the present disclosure may include any of thefirst through twenty-fourth aspects, in which the multifunctionalcatalyst has an acidity of from 1,000 μmol(NH₃)/g to 15,000 μmol(NH₃)/g.

A twenty-sixth aspect of the present disclosure may include any of thefirst through twenty-fifth aspects, in which the multifunctionalcatalyst has a BET surface area of from 300 meters squared per gram to700 meters squared per gram.

A twenty-seventh aspect of the present disclosure may include any of thefirst through twenty-sixth aspects, in which a method for upgradingpyrolysis oil may include contacting the pyrolysis oil with themultifunctional catalyst of any of the first through twenty-sixthaspects at mild reaction conditions comprising reaction temperatures ofless than 500 degrees Celsius and pressures less than 6 megapascals. Thepyrolysis oil may include multi-ring aromatic compounds. Contacting thepyrolysis oil with the multifunctional catalyst at the reactionconditions may convert at least a portion of the multi-ring aromaticcompounds in the pyrolysis oil to one or more C6-C8 aromatic compounds.

In a twenty-eighth aspect of the present disclosure, a method forupgrading pyrolysis oil may include contacting the pyrolysis oil with amultifunctional catalyst at mild reaction conditions comprising reactiontemperatures of less than 500 degrees Celsius (° C.) and pressures lessthan 6 megapascals (MPa). The pyrolysis oil may include multi-ringaromatic compounds. The multifunctional catalyst may be produced by aprocess comprising contacting a hierarchical mesoporous zeolite supportwith a solution comprising at least a first metal catalyst precursor anda second metal catalyst precursor. The hierarchical mesoporous zeolitesupport may have an average pore size of from 2 nanometers to 40nanometers as determined by Barrett-Joyner-Halenda (BJH) analysis, thefirst metal catalyst precursor, the second metal catalyst precursor, orboth, may include a heteropolyacid, and the contacting deposits thefirst metal catalyst precursor and the second catalyst precursor ontoouter surfaces and pore surfaces of the hierarchical mesoporous zeolitesupport to produce a multifunctional catalyst precursor. The process forproducing the multifunctional catalyst may further include removingexcess solution from the multifunctional catalyst precursor andcalcining the multifunctional catalyst precursor to produce themultifunctional catalyst. The multifunctional catalyst comprises atleast a first metal catalyst and a second metal catalyst supported onthe zeolite support. Contact of the pyrolysis oil with themultifunctional catalyst at the reaction conditions may convert at leasta portion of the multi-ring aromatic compounds in the pyrolysis oil toone or more C6-C8 aromatic compounds.

A twenty-ninth aspect of the present disclosure may include either thetwenty-seventh or twenty-eighth aspects, in which the C6-C8 aromaticcompounds include one or more of benzene, toluene, ethylbenzene, xylene,or combinations of these.

A thirtieth aspect of the present disclosure may include any of thetwenty-seventh through twenty-ninth aspects, in which contacting thepyrolysis oil with the multifunctional catalyst at the reactionconditions may convert the portion of the multi-ring aromatic compoundsin the pyrolysis oil to C6-C8 aromatic compounds in a single step,without conducting a subsequent chemical reaction step.

A thirty-first aspect of the present disclosure may include any of thetwenty-seventh through thirtieth aspects, where contacting the pyrolysisoil with the multifunctional catalyst may result a yield of C6-C8aromatic compounds of at least 30 percent (%).

A thirty-second aspect of the present disclosure may include any of thetwenty-seventh through thirty-first aspects, further comprisingseparating an upgraded pyrolysis oil from the multifunctional catalyst.

A thirty-third aspect of the present disclosure may include any of thetwenty-seventh through thirty-second aspects, in which the pyrolysis oilis contacted with the multifunctional catalyst at a temperature of from380 degrees Celsius to 400 degrees Celsius.

A thirty-fourth aspect of the present disclosure may include any of thetwenty-seventh through thirty-third aspects, in which the pyrolysis oilmay be contacted with the multifunctional catalyst at a pressure lessthan or equal to 5 megapascals.

A thirty-fifth aspect of the present disclosure may include any of thetwenty-seventh through thirty-fourth aspects, in which the pyrolysis oilis contacted with the multifunctional catalyst at a pressure of from 0.1megapascal to 5 megapascals.

It should now be understood that various aspects of the multifunctionalcatalyst for upgrading pyrolysis oil, methods of making themultifunctional catalyst for upgrading pyrolysis oil usingheteropolyacids as the metal catalyst precursors, and methods ofupgrading pyrolysis oils using the methods are described and suchaspects may be utilized in conjunction with various other aspects.

Throughout this disclosure, ranges are provided for various propertiesand characteristics of the multifunctional catalyst and variousprocessing parameters and operating conditions for the methods formaking the multifunctional catalyst and upgrading pyrolysis oil. It willbe appreciated that when one or more explicit ranges are provided theindividual values and the sub-ranges formed within the range are alsointended to be provided as providing an explicit listing of all possiblecombinations is prohibitive. For example, a provided range of 1-10 alsoincludes the individual values, such as 1, 2, 3, 4.2, and 6.8, as wellas all the ranges, which may be formed within the provided bounds, suchas 1-8, 2-4, 6-9, and 1.3-5.6.

It should be apparent to those skilled in the art that variousmodifications and variations can be made to the described embodimentswithout departing from the spirit and scope of the claimed subjectmatter. Thus, it is intended that the specification cover themodifications and variations of the various described embodimentsprovided such modification and variations come within the scope of theappended claims and their equivalents.

1. A method of making a multifunctional catalyst for upgrading pyrolysisoil, the method comprising: contacting a hierarchical mesoporous zeolitesupport with a solution comprising at least a first metal catalystprecursor and a second metal catalyst precursor, where: the hierarchicalmesoporous zeolite support has an average pore size of from 2 nanometersto 40 nanometers as determined by Barrett-Joyner-Halenda (BJH) analysis;the first metal catalyst precursor, the second metal catalyst precursor,or both, comprises a heteropolyacid having at least one heteroatomselected from the group consisting of phosphorous, silicon, germanium,arsenic, and combinations of these; and the contacting deposits thefirst metal catalyst precursor and the second metal catalyst precursoronto outer surfaces and pore surfaces of the hierarchical mesoporouszeolite support to produce a multifunctional catalyst precursor;removing excess solution from the multifunctional catalyst precursor;and calcining the multifunctional catalyst precursor to produce themultifunctional catalyst comprising at least a first metal catalyst anda second metal catalyst deposited on the outer surfaces and poresurfaces of the hierarchical mesoporous zeolite support.
 2. The methodof claim 1, in which the hierarchical mesoporous zeolite supportcomprises a hierarchical mesoporous beta zeolite support.
 3. The methodof claim 1, in which the hierarchical mesoporous zeolite support has anaverage pore size of from 5 nanometers to 25 nanometers as determined byBJH analysis.
 4. The method of claim 1, in which the hierarchicalmesoporous zeolite support has a total pore volume of greater than orequal to 0.35 cubic centimeters per gram.
 5. The method of claim 1, inwhich the hierarchical mesoporous zeolite support comprises a molarratio of silica to alumina of from 20 to
 100. 6. The method of claim 1,further comprising producing the hierarchical mesoporous zeolitesupport.
 7. The method of claim 6, in which producing the hierarchicalmesoporous zeolite support comprises converting a microporous parentzeolite into the hierarchical mesoporous zeolite support throughdesilication of the microporous parent zeolite.
 8. The method of claim7, in which desilication of the microporous parent zeolite to producethe hierarchical mesoporous zeolite support comprises: mixing themicroporous zeolite with an aqueous metal hydroxide solution; andheating the microporous zeolite and aqueous metal hydroxide mixture to atemperature of greater than or equal to 100 degrees Celsius to producethe hierarchical mesoporous zeolite support.
 9. The method of claim 1,in which the heteropolyacid comprises: at least one metal selected fromcobalt, molybdenum, vanadium, or combinations of these.
 10. The methodof claim 1, in which the first metal catalyst precursor comprises theheteropolyacid.
 11. The method of claim 1, in which the first metalcatalyst precursor comprises a first heteropolyacid and the second metalcatalyst precursor comprises a second heteropolyacid that is differentfrom the first heteropolyacid. 12-20. (canceled)
 21. The method of claim11, in which the first heteropolyacid or the second heteropolyacid isH₃PMo₁₂O₄₀.
 22. The method of claim 1, in which the heteropolyacidcomprises phosphormolybdic hetereopolyacid having formula H₃PMo₁₂O₄₀.23. The method of claim 1, in which removing the excess solution fromthe multifunctional catalyst precursor comprises filtering or decantingthe excess solution from the multifunctional catalyst precursor anddrying the multifunctional catalyst precursor to remove solvent.
 24. Themethod of claim 1, in which the first metal catalyst comprisesmolybdenum and the second metal catalyst comprises cobalt, where atleast the heteropolyacid includes the molybdenum.
 25. The method ofclaim 1, in which the multifunctional catalyst comprises phosphorousdeposited on the outer surfaces and pore surfaces of the hierarchicalmesoporous zeolite support.
 26. The method of claim 1, in which thehierarchical mesoporous zeolite support comprises an acidity of lessthan 15,000 micromoles of ammonia per gram.